CN110523417B - Carbon shell coated alloy catalyst synthesized based on Cu-BTC and preparation method thereof - Google Patents
Carbon shell coated alloy catalyst synthesized based on Cu-BTC and preparation method thereof Download PDFInfo
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- 239000013148 Cu-BTC MOF Substances 0.000 title claims abstract description 88
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 54
- 239000000956 alloy Substances 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 238000001354 calcination Methods 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 8
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 123
- 239000000243 solution Substances 0.000 claims description 111
- 239000010949 copper Substances 0.000 claims description 80
- 238000005406 washing Methods 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 16
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- HCCMZPLHUHZXCI-UHFFFAOYSA-N [C].[Co].[Cu] Chemical compound [C].[Co].[Cu] HCCMZPLHUHZXCI-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 90
- 239000011259 mixed solution Substances 0.000 description 63
- 239000002244 precipitate Substances 0.000 description 40
- 238000005119 centrifugation Methods 0.000 description 34
- 239000008367 deionised water Substances 0.000 description 27
- 229910021641 deionized water Inorganic materials 0.000 description 27
- 238000004321 preservation Methods 0.000 description 26
- 229910001339 C alloy Inorganic materials 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 238000000227 grinding Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229910018292 Cu2In Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/8926—Copper and noble metals
-
- B01J35/23—
-
- B01J35/398—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
Abstract
The invention discloses a Cu-BTC (copper-cobalt-carbon) synthesis-based carbon shell coated alloy catalyst and a preparation method thereof, belonging to the field of catalyst material preparation. Firstly, synthesizing a Cu-BTC material, calcining the Cu-BTC material at high temperature to form Cu/C composite powder, then placing the Cu/C composite powder in a temperature-controlled oven, slowly heating the temperature to oxidize the Cu/C composite powder into Cu2O/C composite powder, and finally loading different metals on Cu by a high-temperature hydrothermal method2O surface, treating Cu with acid2O is removed to form an internally hollow shell structure, while Cu2Part of Cu ions in O are combined with other metals to form an alloy in the acid treatment process, the carbon film outside the Cu-BTC is not damaged in the whole preparation process, and the finally obtained material is a carbon-coated hollow-shell alloy catalyst. The invention can realize the synthesis of alloy catalysts with different components, and the hollow shell structure of the alloy can greatly improve the exposure of metal atoms; the metal alloy is wrapped by the carbon film, so that the loss of the metal alloy in the using process can be effectively prevented, and the activity and the stability of the alloy catalyst are obviously improved.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of catalyst material preparation, and particularly relates to a carbon shell coated alloy catalyst synthesized based on Cu-BTC and a preparation method thereof.
[ background of the invention ]
The excessive consumption of fossil energy has been a major factor hindering the progress and technological development of human society and is one of the major sources of environmental pollution. Since the 21 st century, all countries in the world have been striving to develop new clean energy technologies, such as: solar energy, hydrogen/oxygen production by catalytic water, fuel cell power generation and the like, wherein the development and the use of a catalyst material are one of key materials for ensuring the commercial use of the energy technologies.
Theoretically, a catalyst refers to a substance which can change the chemical reaction rate of reactants and has no change in the quality or chemical properties, and in fact, the catalyst is often dissolved, lost, poisoned or even completely deactivated in the actual use process due to the complex situation in the chemical reaction. Therefore, it becomes important to develop a catalyst with high performance and stability.
In recent years, alloying and structural design have been considered as main means for effectively solving the problems of the above-mentioned catalysts. The reason is that the electronic structure of the catalyst can be influenced after different metals are alloyed, the stability in the catalysis process can be obviously improved, and the catalysis performance is changed. If other means are adopted to control the structural appearance of the metal alloy while alloying so as to expose more surfaces, the activity of the catalyst can be further improved.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provides a carbon shell coated alloy catalyst based on Cu-BTC synthesis and a preparation method thereof; the hollow shell structure of the alloy prepared by the preparation method can greatly improve the exposure of metal atoms on one hand, and in addition, the metal alloy is wrapped by the carbon film and can effectively prevent the loss of the metal alloy in the catalysis process, so that the catalytic activity and the stability of the metal alloy are obviously improved, and the hollow shell structure has higher practical value.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a carbon shell coated alloy catalyst synthesized based on Cu-BTC has a structure that metal M and Cu are coated in a carbon hollow shell; the metal M is other metal except Cu; the carbon shell is in a polyhedral structure.
Preferably, the metal M is a single metal or a multi-component alloy.
A preparation method of a carbon shell coated alloy catalyst based on Cu-BTC synthesis comprises the following steps:
(1) calcining powdery Cu-BTC to generate Cu/C composite powder, oxidizing the Cu/C composite powder to generate Cu2An O/C composite powder;
(2) mixing Cu2Dissolving the O/C composite powder in water to form Cu2O/C aqueous solution in Cu2Adding metal salt into the O/C aqueous solution, and then adding sodium polyacrylate to adjust the pH value of the solution to 8-9 to form a reaction system; obtaining a reaction product solution after a reaction system undergoes a hydrothermal reaction, adjusting the pH value of the reaction product solution to 1.5-3 by nitric acid to obtain an acidified reaction product solution, centrifuging the acidified reaction product solution, and washing the centrifuged productAnd drying to obtain the carbon shell coated alloy catalyst.
The invention is further improved in that:
preferably, in the step (1), the calcination temperature of the powdery Cu-BTC is 500-700 ℃, and the calcination time is 1-3 h.
Preferably, in the step (1), the oxidation temperature of the Cu/C composite powder is 70-90 ℃, and the oxidation time is 7-9 h.
Preferably, in step (2), Cu2In O/C aqueous solution, Cu2The concentration of O/C is (0.1-0.6) mg/mL.
Preferably, in the step (2), the hydrothermal reaction temperature is 110-.
Preferably, in the step (1), the powdery Cu-BTC is prepared by dissolving copper nitrate trihydrate in methanol to form a solution A; dissolving polyvinylpyrrolidone and 1,3, 5-benzene tricarboxylic acid in methanol to form a solution B; and after the solution A and the solution B are subjected to respective ultrasonic dispersion, mixing the solution A and the solution B and continuously stirring to form process Cu-BTC, centrifuging the process Cu-BTC to obtain a centrifugal product, and washing and drying the centrifugal product to form powdery Cu-BTC.
Preferably, in the solution A, the mixing ratio of the copper nitrate trihydrate and the methanol is (2-10) g: (50-200) mL; in the solution B, the mixing ratio of polyvinylpyrrolidone to methanol is (0.5-2) g: (50-200) mL, the mixing ratio of 1.3.5-benzene tricarboxylic acid and methanol is (1.5-5) g: (50-200) mL.
Preferably, the mixing volume ratio of the solution A and the solution B is 1: 1.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a carbon shell coated alloy catalyst synthesized based on Cu-BTC, wherein the carbon shell is internally coated with an alloy catalyst, the carbon shell is used as a framework structure and is arranged at the periphery of the whole catalyst, the interior of the carbon shell is coated with the alloy, the alloy in the interior is an alloy formed by Cu and M, and the alloy type of the catalyst can be adjusted according to different application fields because M can be any alloy in the structure; because the alloy is wrapped in the carbon shell, the carbon shell has a stable structure, so that the catalyst can effectively prevent the alloy from being corroded and lost in the catalysis process, thereby remarkably improving the catalytic activity and stability of the catalyst.
Furthermore, the metal M can be a monobasic metal or a multi-component alloy, and the type and the quantity of the metal M can be adjusted according to the application field and the requirements of the catalyst, so that the application range of the carbon shell coated alloy catalyst is wide.
The invention also discloses a preparation method of the carbon shell coated alloy catalyst based on Cu-BTC synthesis, which comprises the steps of calcining Cu-BTC into Cu/C composite powder, and oxidizing the Cu/C composite powder into Cu2An O/C composite powder; by adding in Cu2And adding metal salt into the O/C aqueous solution to form a reaction system, and carrying out hydrothermal reaction on the reaction system to obtain a carbon shell coated with an alloy catalyst. In the preparation process, the connecting bond of the internal Cu and C of the powdery Cu-BTC is broken in the calcining process, so that the Cu in the obtained Cu/C composite is coated by the C, and then the C shell coated Cu is formed in the oxidizing process2The structure of O; by adding metal salts to Cu2In the O aqueous solution, the pH of the whole reaction system is firstly adjusted to be alkaline, the whole reaction system is in a reducing environment, and the added metal ions are used for dissolving Cu2Reducing Cu in O, and removing Cu in the carbon shell by acidification2O, finally forming a carbon shell coated alloy catalyst structure; the framework carbon film outside the Cu-BTC cannot be damaged in the whole preparation process, and the alloy is stably wrapped in the carbon shell, so that the preparation process is novel and has wide application prospect.
[ description of the drawings ]
FIG. 1 is an XRD pattern of the product shown in example 1;
FIG. 2 is an SEM and EDS spectra of the morphology of the product shown in example 1;
wherein, the picture (a) is an SEM picture; (b) the figure is an EDS diagram;
FIG. 3 is a TEM spectrum of the product shown in example 1;
FIG. 4 is an XRD pattern of the product shown in example 2;
FIG. 5 is an SEM and EDS spectra of the morphology of the product shown in example 2;
wherein, the picture (a) is an SEM picture; (b) the figure is an EDS diagram;
FIG. 6 is a TEM spectrum of the product shown in example 2.
[ detailed description ] embodiments
The invention is further described in detail with reference to the accompanying drawings and specific examples, and discloses a carbon shell coated alloy catalyst based on Cu-BTC synthesis and a preparation method thereof, wherein the preparation method specifically comprises the following steps:
Step 2, putting the prepared powdery Cu-BTC into a vacuum tubeCalcining for 1-3h in an inert atmosphere in a formula furnace, wherein the calcining temperature is 500-700 ℃, the heating rate is 2 ℃/min, and Cu/C composite powder is obtained after calcining, and the inert atmosphere is 99.9% of argon; grinding the Cu/C composite powder obtained by calcination, then placing the powder into a temperature-controlled oven to slowly raise the temperature for oxidation, wherein the temperature-controlled oven is in an air atmosphere, the temperature raising rate is 15 ℃/h, the heat preservation temperature is 70-90 ℃, and the heat preservation time is 7-9h, so that Cu is formed2An O/C composite powder; in the step process, the connecting bond of the internal Cu and the C of the powdery Cu-BTC is broken in the calcining process, so that the Cu in the obtained Cu/C composite is coated by the C, the C outside the Cu has more holes due to the structure of the C, and the Cu is oxidized in the subsequent temperature-controlled oven heating oxidation process to finally form the Cu2O/C composite powder.
The invention discloses a preparation method of a carbon-coated vacant-shell PtPdCu alloy catalyst based on Cu-BTC synthesis2O/C, finally, loading M on Cu by a high-temperature hydrothermal method2O surface, treating Cu with acid2Removing O to form a hollow shell structure with part of Cu2Cu ions in O are combined with M in the acid treatment process to form a target alloy, and the whole preparation process cannot damage a carbon film outside the Cu-BTC, so that the finally obtained material is a carbon-coated hollow MCu alloy catalyst.
The Cu-BTC material is synthesized firstly, and then the carbon-coated hollow shell alloy catalyst is prepared through the steps of calcining, oxidizing, high-temperature hydrothermal and the like, the synthesis of alloy catalysts with different components is realized by adding different metal salts, the exposure of metal atoms can be greatly improved by the hollow shell structure of the alloy, in addition, the metal alloy is wrapped by a carbon film, the loss in the catalytic process can be effectively prevented, the catalytic activity and the stability of the alloy are obviously improved, and the carbon-coated hollow shell alloy catalyst has higher practical value.
Example 1
Two portions of 90mL of methanol were weighed, first5g of copper nitrate trihydrate (Cu (NO)3)2·3H2O) was dissolved in one portion of methanol and vigorously stirred (solution A), and 1.5g of polyvinylpyrrolidone and 3.2g of 1.3.5-benzenetricarboxylic acid were dissolved in the other portion of methanol (solution B), after 10min of sonication, solution A was poured into a separatory funnel, dropping the solution into the solution B at the speed of 300 mu L/min, continuously stirring, after the dropping is finished, stirring for 36h to form Cu-BTC, centrifuging the mixed solution at 7000r/min to collect precipitate, repeatedly washing with ethanol/deionized water mixed solution for 8min each time, centrifuging for 6 times at a volume ratio of ethanol to deionized water of 1:1, then, along with the increase of the washing times, the proportion of ethanol in the mixed solution is increased at a constant speed until the 6 th washing, the used solution is pure ethanol. Finally, placing the precipitate in a vacuum oven for drying at normal temperature, and grinding into powder for later use;
putting the prepared Cu-BTC into a vacuum tube furnace for calcination, wherein the protective gas used for calcination is argon with the concentration of 99.9 percent, the gas flow rate is 120, the heating rate is 2 ℃/min, the calcination temperature is 600 ℃, the heat preservation time is 2 hours, taking out the Cu-BTC after being cooled to room temperature, grinding the Cu-BTC, putting the ground Cu-BTC into a temperature-controlled oven for heating up and oxidizing, the heating rate is 15 ℃/h, the heat preservation temperature is 80 ℃, and the heat preservation time is 8 hours, so that the Cu-BTC is formed2O/C composite powder.
Weighing 15mg of Cu2Dissolving the O/C composite powder in 25mL of water, adding 5mg of palladium chloride under continuous stirring, then adjusting the pH value of the mixed solution to 8.5 by using a 50% sodium polyacrylate solution, continuously stirring for 20min, pouring the solution into a reaction kettle, sealing and carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 6 h. And after the reaction is finished, placing the mixed solution on a magnetic stirrer, dripping nitric acid while stirring to adjust the pH value of the solution to 2.5, then placing the mixed solution in a centrifuge for centrifugation to collect precipitates, repeatedly washing the precipitates by using an ethanol/deionized water (1:1) mixed solution, wherein the centrifugation speed is 8000r/min, the centrifugation time is 15min each time, the washing frequency is 5 times, and after the centrifugation is finished, placing the precipitates in a vacuum drying oven for drying at 60 ℃ for 12h to obtain the PdCu @ C alloy catalyst.
FIG. 1 is an XRD pattern of PtCu @ C alloy catalyst obtained in example 1 of the present invention, and it can be seen that the substance prepared in example 1 has XRD characteristic peaks between the Pt characteristic peak (JCPDS No.04-0802) and the Cu characteristic peak (JCPDS No.04-0836), and exhibits typical metal combination property.
FIG. 2 is SEM and EDS spectra of PtCu @ C alloy catalyst obtained in example 1 of the present invention, wherein (a) is SEM image, and (b) is EDS image, from which it can be seen that the PtCu @ C alloy produced has a uniform polyhedral structure, and Table 1 shows elements and their contents in EDS image, from which it can be seen that Pt element and Cu element are uniformly distributed.
Table 1 PtCu @ C alloy catalyst element content prepared in example 1
FIG. 3 is a TEM spectrum of the PtCu @ C alloy catalyst obtained in example 1 of the present invention, and it can be seen that the prepared PtCu @ C alloy has a hollow shell morphology and is surrounded by a carbon film.
Example 2
Two 80mL portions of methanol were weighed, first 5g of copper nitrate trihydrate (Cu (NO)3)2·3H2O) is dissolved in one of the portions of methanol and vigorously stirred (solution A), 1.3g of polyvinylpyrrolidone and 3g of 1.3.5-benzenetricarboxylic acid are dissolved in the other portion of methanol (solution B), after 10min of ultrasound, the solution A is poured into a separating funnel, dropping the solution into the solution B at the speed of 300 mu L/min, continuously stirring, after the dropping is finished, stirring for 28h to form Cu-BTC, centrifuging the mixed solution at 7000r/min to collect precipitate, repeatedly washing with mixed solution of ethanol and deionized water, centrifuging for 8min each time for 6 times at a volume ratio of ethanol to deionized water of 1:1, then, along with the increase of the washing times, the proportion of ethanol in the mixed solution is increased at a constant speed until the 6 th washing, the used solution is pure ethanol. Finally, the precipitate was placed under vacuumDrying in a drying oven at normal temperature, and grinding into powder for later use;
putting the prepared Cu-BTC into a vacuum tube furnace for calcination, wherein the protective gas used for calcination is argon with the concentration of 99.9 percent, the gas flow rate is 100, the heating rate is 2 ℃/min, the calcination temperature is 600 ℃, the heat preservation time is 2 hours, taking out the Cu-BTC after being cooled to room temperature, grinding the Cu-BTC, putting the ground Cu-BTC into a temperature-controlled oven for heating up and oxidizing, the heating rate is 15 ℃/h, the heat preservation temperature is 80 ℃, and the heat preservation time is 8 hours, so that the Cu is formed2O/C composite powder.
10mg of Cu are weighed2Dissolving the O/C composite powder in 20mL of water, adding 3mg of palladium chloride and 3mg of potassium chloroplatinite under continuous stirring, then adjusting the pH value of the mixed solution to 9 by using a 50% sodium polyacrylate solution, continuously stirring for 15min, pouring the solution into a reaction kettle, sealing and carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 6 h. And after the reaction is finished, placing the mixed solution on a magnetic stirrer, dripping nitric acid while stirring to adjust the pH value of the solution to 2, then placing the mixed solution in a centrifuge for centrifugation to collect precipitates, repeatedly washing the precipitates by using an ethanol/deionized water (1:1) mixed solution, wherein the centrifugation speed is 8000r/min, the centrifugation time is 15min each time, the washing times are 4 times, and after the centrifugation is finished, placing the precipitates in a vacuum drying oven for drying at 60 ℃ for 12h to obtain the PtPdCu @ C alloy catalyst.
FIG. 4 is an XRD pattern of the PtPdCu @ C alloy catalyst obtained in example 2 of the present invention, and it can be seen that the XRD characteristic peak of the substance prepared in example 2 is between the Pt characteristic peak (JCPDS No.04-0802), the Pd characteristic peak (JCPDS No.46-1043) and the Cu characteristic peak (JCPDS No.04-0836), and a typical resultant metal property is exhibited.
FIG. 5 is SEM and EDS spectra of PtPdCu @ C alloy catalyst obtained in example 2 of the present invention, wherein (a) is a SEM image and (b) is an EDS image; as can be seen from the figure (a), the prepared PtPdCu @ C alloy has uniform polyhedral shape and size; referring to table 2 for the element content of the PtPdCu @ C alloy catalyst prepared in example 2, it can be seen from table 2 and the graph (b) that the Pt element, Pd element, and Cu element are present at the same time.
Table 2 PtPdCu @ C alloy catalyst element content prepared in example 2
| Element(s) | By weight percent | By atomic weight% |
| C K | 13.56 | 50.78 |
| O K | 6.19 | 17.41 |
| Cu L | 12.50 | 8.85 |
| Pt M | 29.59 | 6.82 |
| Pd L | 38.16 | 16.14 |
Fig. 6 is a TEM spectrum of the PtPdCu @ C alloy catalyst obtained in example 2 of the present invention, and it can be seen that the prepared PtPdCu @ C alloy also shows a structure in which the PtPdCu hollow shell alloy is surrounded by a carbon film.
Example 3
Two 100mL portions of methanol were weighed, first with 8g of copper nitrate trihydrate (Cu (NO)3)2·3H2O) is dissolved in one portion of methanol and stirred vigorously (solution A), 2g of polyDissolving vinylpyrrolidone and 3g of 1.3.5-benzenetricarboxylic acid in another part of methanol (solution B), performing ultrasonic treatment for 12min, pouring the solution A into a separating funnel, dripping the solution A into the solution B at the speed of 300 mu L/min and continuously stirring, continuously stirring for 28h after dripping is finished to form Cu-BTC, centrifuging the mixed solution at 7000r/min after stirring is finished, collecting precipitates, repeatedly washing with an ethanol/deionized water mixed solution, wherein the centrifugation time is 8min each time, the centrifugation washing frequency is 6 times, the volume ratio of ethanol to deionized water in the mixed solution for the first washing is 1:1, then, increasing the proportion of ethanol in the mixed solution at a constant speed along with the increase of the washing frequency until the 6 th washing is finished, and the used solution is pure ethanol. Finally, placing the precipitate in a vacuum oven for drying at normal temperature, and grinding into powder for later use;
putting the prepared Cu-BTC into a vacuum tube furnace for calcination, wherein the protective gas used for calcination is argon with the concentration of 99.9 percent, the gas flow rate is 100, the heating rate is 2 ℃/min, the calcination temperature is 600 ℃, the heat preservation time is 2 hours, taking out the Cu-BTC after being cooled to room temperature, grinding the Cu-BTC, putting the ground Cu-BTC into a temperature-controlled oven for heating up and oxidizing, the heating rate is 15 ℃/h, the heat preservation temperature is 80 ℃, and the heat preservation time is 8 hours, so that the Cu is formed2O/C composite powder.
Weighing 8mg of Cu2Dissolving O/C powder in 15mL of water, adding 3mg of anhydrous ruthenium chloride under continuous stirring, then adjusting the pH value of the mixed solution to 9 by using a 50% sodium polyacrylate solution, continuing stirring for 15min, pouring the solution into a reaction kettle, sealing and carrying out hydrothermal reaction at the reaction temperature of 120 ℃ for 8 h. And after the reaction is finished, placing the mixed solution on a magnetic stirrer, dripping nitric acid while stirring to adjust the pH value of the solution to 2, then placing the mixed solution in a centrifuge for centrifugation to collect precipitates, repeatedly washing the precipitates by using an ethanol/deionized water (1:1) mixed solution, wherein the centrifugation speed is 8000r/min, the centrifugation time is 15min each time, the washing times are 4 times, and after the centrifugation is finished, placing the precipitates in a vacuum drying oven for drying at 60 ℃ for 12h to obtain the RuCu @ C catalyst.
Example 4
Two 500mL portions of methanol were weighed, first with 2g of copper nitrate trihydrate (Cu (NO)3)2·3H2O) is dissolved in one part of methanol and mixedStirring vigorously (solution A), dissolving 1g of polyvinylpyrrolidone and 2g of 1.3.5-benzenetricarboxylic acid in another part of methanol (solution B), performing ultrasonic treatment for 10min, pouring the solution A into a separating funnel, dripping the solution A into the solution B at the speed of 300 mu L/min, continuously stirring for 28h to form Cu-BTC, after stirring, centrifuging the mixed solution at 7000r/min to collect precipitates, repeatedly washing with an ethanol/deionized water mixed solution, wherein the centrifuging time is 8min each time, the centrifuging and washing times are 6 times, the volume ratio of ethanol to deionized water in the mixed solution for the first washing is 1:1, and then, the proportion of ethanol in the mixed solution is increased at a constant speed along with the increase of the washing times until the 6 th washing time, the used solution is pure ethanol. Finally, placing the precipitate in a vacuum oven for drying at normal temperature, and grinding into powder for later use;
putting the prepared Cu-BTC into a vacuum tube furnace for calcination, wherein the protective gas used for calcination is argon with the concentration of 99.9 percent, the gas flow rate is 100, the heating rate is 2 ℃/min, the calcination temperature is 550 ℃, the heat preservation time is 2 hours, taking out the Cu-BTC after the Cu-BTC is cooled to room temperature, grinding the Cu-BTC, putting the ground Cu-BTC into a temperature-controlled oven for heating up and oxidizing, the heating rate is 15 ℃/h, the heat preservation temperature is 90 ℃, and the heat preservation time is 7 hours, so that the Cu is formed2O/C composite powder.
6mg of Cu are weighed2Dissolving the O/C composite powder in 20mL of water, adding 3mg of palladium chloride and 3mg of potassium chloroplatinite under continuous stirring, adjusting the pH value of the mixed solution to 9 by using a 50% sodium polyacrylate solution, continuously stirring for 15min, pouring the solution into a reaction kettle, sealing and carrying out hydrothermal reaction at the reaction temperature of 115 ℃ for 5 h. And after the reaction is finished, placing the mixed solution on a magnetic stirrer, dripping nitric acid while stirring to adjust the pH value of the solution to 2, then placing the mixed solution in a centrifuge for centrifugation to collect precipitates, repeatedly washing the precipitates by using an ethanol/deionized water (1:1) mixed solution, wherein the centrifugation speed is 8000r/min, the centrifugation time is 15min each time, the washing times are 4 times, and after the centrifugation is finished, placing the precipitates in a vacuum drying oven for drying at 60 ℃ for 12h to obtain the PtPdCu @ C alloy catalyst.
Example 5
Two 200mL portions of methanol were weighed, first with 10g of copper nitrate trihydrate (Cu (NO)3)2·3H2O) was dissolved in one portion of methanol and vigorously stirred (solution A), then 1.8g of polyvinylpyrrolidone and 5g of 1.3.5-benzenetricarboxylic acid were dissolved in the other portion of methanol (solution B), after 10min of sonication, solution A was poured into a separatory funnel, dropping the solution into the solution B at the speed of 300 mu L/min, continuously stirring, after the dropping is finished, stirring for 28h to form Cu-BTC, centrifuging the mixed solution at 7000r/min to collect precipitate, repeatedly washing with mixed solution of ethanol and deionized water, centrifuging for 8min each time for 6 times at a volume ratio of ethanol to deionized water of 1:1, then, along with the increase of the washing times, the proportion of ethanol in the mixed solution is increased at a constant speed until the 6 th washing, the used solution is pure ethanol. Finally, placing the precipitate in a vacuum oven for drying at normal temperature, and grinding into powder for later use;
putting the prepared Cu-BTC into a vacuum tube furnace for calcination, wherein the protective gas used for calcination is argon with the concentration of 99.9 percent, the gas flow rate is 100, the heating rate is 2 ℃/min, the calcination temperature is 700 ℃, the heat preservation time is 3h, taking out the Cu-BTC after being cooled to room temperature, grinding the Cu-BTC, putting the ground Cu-BTC into a temperature-controlled oven for heating up and oxidizing, the heating rate is 15 ℃/h, the heat preservation temperature is 90 ℃, and the heat preservation time is 7h, so that the Cu is formed2O/C composite powder.
Weighing 1mg of Cu2Dissolving the O/C composite powder in 10mL of water, adding 3mg of palladium chloride and 3mg of potassium chloroplatinite under continuous stirring, then adjusting the pH value of the mixed solution to 9 by using a 50% sodium polyacrylate solution, continuously stirring for 15min, pouring the solution into a reaction kettle, sealing and carrying out hydrothermal reaction at the reaction temperature of 110 ℃ for 7 h. And after the reaction is finished, placing the mixed solution on a magnetic stirrer, dripping nitric acid while stirring to adjust the pH value of the solution to 2, then placing the mixed solution in a centrifuge for centrifugation to collect precipitates, repeatedly washing the precipitates by using an ethanol/deionized water (1:1) mixed solution, wherein the centrifugation speed is 8000r/min, the centrifugation time is 15min each time, the washing times are 4 times, and after the centrifugation is finished, placing the precipitates in a vacuum drying oven for drying at 60 ℃ for 12h to obtain the PtPdCu @ C alloy catalyst.
Example 6
Weighing machineTwo 150mL portions of methanol were first washed with 3g of copper nitrate trihydrate (Cu (NO)3)2·3H2O) was dissolved in one portion of methanol and vigorously stirred (solution A), 0.5g of polyvinylpyrrolidone and 1.5g of 1.3.5-benzenetricarboxylic acid were dissolved in the other portion of methanol (solution B), and after 10min of sonication, solution A was poured into a separatory funnel, dropping the solution into the solution B at the speed of 300 mu L/min, continuously stirring, after the dropping is finished, stirring for 28h to form Cu-BTC, centrifuging the mixed solution at 7000r/min to collect precipitate, repeatedly washing with mixed solution of ethanol and deionized water, centrifuging for 8min each time for 6 times at a volume ratio of ethanol to deionized water of 1:1, then, along with the increase of the washing times, the proportion of ethanol in the mixed solution is increased at a constant speed until the 6 th washing, the used solution is pure ethanol. Finally, placing the precipitate in a vacuum oven for drying at normal temperature, and grinding into powder for later use;
putting the prepared Cu-BTC into a vacuum tube furnace for calcination, wherein the protective gas used for calcination is argon with the concentration of 99.9 percent, the gas flow rate is 100, the heating rate is 2 ℃/min, the calcination temperature is 500 ℃, the heat preservation time is 1h, taking out the Cu-BTC after being cooled to room temperature, grinding the Cu-BTC, putting the ground Cu-BTC into a temperature-controlled oven for heating and oxidizing, the heating rate is 15 ℃/h, the heat preservation temperature is 70 ℃, and the heat preservation time is 8h, so that the Cu is formed2O/C composite powder.
Weighing 8mg of Cu2Dissolving the O/C composite powder in 20mL of water, adding 3mg of palladium chloride and 3mg of potassium chloroplatinite under continuous stirring, then adjusting the pH value of the mixed solution to 9 by using a 50% sodium polyacrylate solution, continuously stirring for 15min, pouring the solution into a reaction kettle, sealing and carrying out hydrothermal reaction at the reaction temperature of 130 ℃ for 5 h. And after the reaction is finished, placing the mixed solution on a magnetic stirrer, dripping nitric acid while stirring to adjust the pH value of the solution to 2, then placing the mixed solution in a centrifuge for centrifugation to collect precipitates, repeatedly washing the precipitates by using an ethanol/deionized water (1:1) mixed solution, wherein the centrifugation speed is 8000r/min, the centrifugation time is 15min each time, the washing times are 4 times, and after the centrifugation is finished, placing the precipitates in a vacuum drying oven for drying at 60 ℃ for 12h to obtain the PtPdCu @ C alloy catalyst.
Example 7
Two 120mL portions of methanol were weighed, first with 4g of copper nitrate trihydrate (Cu (NO)3)2·3H2O) is dissolved in one of the portions of methanol and vigorously stirred (solution A), 2g of polyvinylpyrrolidone and 4g of 1.3.5-benzenetricarboxylic acid are dissolved in the other portion of methanol (solution B), after 10min of ultrasound, solution A is poured into a separating funnel, dropping the solution into the solution B at the speed of 300 mu L/min, continuously stirring, after the dropping is finished, stirring for 28h to form Cu-BTC, centrifuging the mixed solution at 7000r/min to collect precipitate, repeatedly washing with mixed solution of ethanol and deionized water, centrifuging for 8min each time for 6 times at a volume ratio of ethanol to deionized water of 1:1, then, along with the increase of the washing times, the proportion of ethanol in the mixed solution is increased at a constant speed until the 6 th washing, the used solution is pure ethanol. Finally, placing the precipitate in a vacuum oven for drying at normal temperature, and grinding into powder for later use;
putting the prepared Cu-BTC into a vacuum tube furnace for calcination, wherein the protective gas used for calcination is argon with the concentration of 99.9 percent, the gas flow rate is 100, the heating rate is 2 ℃/min, the calcination temperature is 650 ℃, the heat preservation time is 1h, taking out the Cu-BTC after being cooled to room temperature, grinding the Cu-BTC, putting the ground Cu-BTC into a temperature-controlled oven for heating up and oxidizing, the heating rate is 15 ℃/h, the heat preservation temperature is 85 ℃, and the heat preservation time is 7h, so that the Cu is formed2O/C composite powder.
Weighing 12mg of Cu2Dissolving the O/C composite powder in 20mL of water, adding 3mg of palladium chloride and 3mg of potassium chloroplatinite under continuous stirring, then adjusting the pH value of the mixed solution to 9 by using a 50% sodium polyacrylate solution, continuously stirring for 15min, pouring the solution into a reaction kettle, sealing and carrying out hydrothermal reaction at the reaction temperature of 125 ℃ for 7 h. After the reaction is finished, placing the mixed solution on a magnetic stirrer, dripping nitric acid while stirring to adjust the pH value of the solution to 2, then placing the mixed solution in a centrifuge for centrifugation to collect precipitates, repeatedly washing the precipitates by using an ethanol/deionized water (1:1) mixed solution, wherein the centrifugation speed is 8000r/min, the centrifugation time is 15min each time, the washing times are 4 times, after the centrifugation is finished, placing the precipitates in a vacuum drying oven for drying for 12 hours at the temperature of 60 ℃,thus obtaining the PtPdCu @ C alloy catalyst.
Example 8
Two 180mL portions of methanol were weighed, first with 9g of copper nitrate trihydrate (Cu (NO)3)2·3H2O) was dissolved in one portion of methanol and vigorously stirred (solution A), 0.8g of polyvinylpyrrolidone and 3.5g of 1.3.5-benzenetricarboxylic acid were dissolved in the other portion of methanol (solution B), and after 10min of sonication, solution A was poured into a separatory funnel, dropping the solution into the solution B at the speed of 300 mu L/min, continuously stirring, after the dropping is finished, stirring for 28h to form Cu-BTC, centrifuging the mixed solution at 7000r/min to collect precipitate, repeatedly washing with mixed solution of ethanol and deionized water, centrifuging for 8min each time for 6 times at a volume ratio of ethanol to deionized water of 1:1, then, along with the increase of the washing times, the proportion of ethanol in the mixed solution is increased at a constant speed until the 6 th washing, the used solution is pure ethanol. Finally, placing the precipitate in a vacuum oven for drying at normal temperature, and grinding into powder for later use;
putting the prepared Cu-BTC into a vacuum tube furnace for calcination, wherein the protective gas used for calcination is argon with the concentration of 99.9 percent, the gas flow rate is 100, the heating rate is 2 ℃/min, the calcination temperature is 700 ℃, the heat preservation time is 3h, taking out the Cu-BTC after being cooled to room temperature, grinding the Cu-BTC, putting the ground Cu-BTC into a temperature-controlled oven for heating and oxidizing, the heating rate is 15 ℃/h, the heat preservation temperature is 90 ℃, and the heat preservation time is 9h, so that the Cu is formed2O/C composite powder.
10mg of Cu are weighed2Dissolving the O/C composite powder in 20mL of water, adding 3mg of palladium chloride and 3mg of potassium chloroplatinite under continuous stirring, then adjusting the pH value of the mixed solution to 9 by using a 50% sodium polyacrylate solution, continuously stirring for 15min, pouring the solution into a reaction kettle, sealing and carrying out hydrothermal reaction at the reaction temperature of 110 ℃ for 8 h. After the reaction is finished, placing the mixed solution on a magnetic stirrer, dripping nitric acid while stirring to adjust the pH value of the solution to 2, then placing the mixed solution in a centrifuge for centrifugation to collect precipitates, repeatedly washing the precipitates with an ethanol/deionized water (1:1) mixed solution, wherein the centrifugation speed is 8000r/min, the centrifugation time is 15min each time, the washing times are 4 times, and the centrifugation is finishedAnd then, drying the precipitate in a vacuum drying oven at 60 ℃ for 12h to obtain the PtPdCu @ C alloy catalyst.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a carbon shell coated alloy catalyst based on Cu-BTC synthesis is characterized by comprising the following steps:
(1) calcining powdery Cu-BTC to generate Cu/C composite powder, oxidizing the Cu/C composite powder to generate Cu2An O/C composite powder;
(2) mixing Cu2Dissolving the O/C composite powder in water to form Cu2O/C aqueous solution in Cu2Adding metal salt into the O/C aqueous solution, and then adding sodium polyacrylate to adjust the pH value of the solution to 8-9 to form a reaction system; obtaining a reaction product solution after a reaction system undergoes a hydrothermal reaction, adjusting the pH value of the reaction product solution to 1.5-3 by nitric acid to obtain an acidified reaction product solution, centrifuging the acidified reaction product solution, washing and drying the centrifuged product to obtain the carbon shell coated alloy catalyst.
2. The method as claimed in claim 1, wherein the calcination temperature of the powdered Cu-BTC is 500-700 ℃ and the calcination time is 1-3h in step (1).
3. The preparation method of the carbon shell coated alloy catalyst synthesized based on Cu-BTC as claimed in claim 1, wherein in the step (1), the oxidation temperature of the Cu/C composite powder is 70-90 ℃ and the oxidation time is 7-9 h.
4. The method for preparing a carbon shell coated alloy catalyst based on Cu-BTC synthesis as claimed in claim 1, wherein in the step (2), Cu2O/C aqueous solutionIn, Cu2The concentration of O/C is (0.1-0.6) mg/mL.
5. The method as claimed in claim 1, wherein the hydrothermal reaction temperature in step (2) is 110-130 ℃ and the hydrothermal reaction time is 5-8 h.
6. The method for preparing a carbon shell coated alloy catalyst based on Cu-BTC synthesis as claimed in claim 1, wherein in the step (1), the powdered Cu-BTC is prepared by dissolving copper nitrate trihydrate in methanol to form a solution A; dissolving polyvinylpyrrolidone and 1,3, 5-benzene tricarboxylic acid in methanol to form a solution B; and after the solution A and the solution B are subjected to respective ultrasonic dispersion, mixing the solution A and the solution B and continuously stirring to form process Cu-BTC, centrifuging the process Cu-BTC to obtain a centrifugal product, and washing and drying the centrifugal product to form powdery Cu-BTC.
7. The method for preparing a carbon shell coated alloy catalyst based on Cu-BTC synthesis as claimed in claim 6, wherein the mixing ratio of the copper nitrate trihydrate and methanol in the solution A is (2-10) g: (50-200) mL; in the solution B, the mixing ratio of polyvinylpyrrolidone to methanol is (0.5-2) g: (50-200) mL, and the mixing ratio of the 1,3, 5-benzenetricarboxylic acid and the methanol is (1.5-5) g: (50-200) mL.
8. The method for preparing a carbon shell coated alloy catalyst based on Cu-BTC synthesis as claimed in claim 6, wherein the mixing volume ratio of the solution A and the solution B is 1: 1.
9. A carbon shell coated alloy catalyst based on Cu-BTC synthesis prepared by the preparation method of any one of claims 1 to 8, wherein the carbon shell coated alloy catalyst has a structure in which a metal M and Cu are coated in a carbon empty shell; the metal M is other metal except Cu; the carbon shell is in a polyhedral structure.
10. The carbon shell coated alloy catalyst based on Cu-BTC synthesis of claim 9, wherein the metal M is a mono-or multi-metal alloy.
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