CN112342422A - Copper-silicon alloy material and preparation method and application thereof - Google Patents
Copper-silicon alloy material and preparation method and application thereof Download PDFInfo
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- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910000676 Si alloy Inorganic materials 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 122
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 15
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910018067 Cu3Si Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 235000014653 Carica parviflora Nutrition 0.000 claims description 3
- 241000243321 Cnidaria Species 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 16
- 229910052573 porcelain Inorganic materials 0.000 description 16
- 230000007480 spreading Effects 0.000 description 16
- 238000003892 spreading Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
- C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
-
- 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
- B01J23/72—Copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/18—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on silicides
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Abstract
The invention discloses a preparation method of a copper-silicon alloy material, which comprises the following steps: step 1: uniformly mixing Cu powder and Si powder to obtain a mixture; in the mixture, the mass percentage content of Cu powder is 60-80%; step 2: putting the mixture into a high-temperature furnace, pretreating the mixture in an inert atmosphere and calcining the mixture at the high temperature of 700-1300 ℃ for 2-10 h to obtain the copper-silicon alloy material Cu3And (3) Si. Copper silicon alloy material (Cu) prepared by the invention3Si) has good copper-silicon dispersibility, strong copper-silicon interaction and good stability, and is a catalyst with great potentialAn agent and an electrode material; the copper-silicon alloy material can be used as a catalyst for synthesizing trimethoxy silane. Meanwhile, Cu of the present invention3According to the preparation method of Si, the product does not need to be purified, only high-temperature calcination is needed, the reactants are cheap and easy to obtain, the process is simple, the repeatability is good, and the preparation method is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of material synthesis, and relates to a copper-silicon alloy material, and a preparation method and application thereof.
Background
The metal silicide has wide application in the fields of device packaging, organic synthesis, Internet and the like, in particular to Cu3Si, as an alloy material, has a wide application prospect in the fields of solar cells, electrode materials, novel functional materials, organic silicon and the like due to its ability to well hinder the movement of copper atoms (m.klementov et al, j.cryst.growth.2017, 465, 6-11).
At present, the existing literature reports only about the low Cu content3Synthesis of a mixture of Si. For example, Zhang et al disclose a Cu3The preparation method of Si comprises the steps of firstly preparing Mg2Mixing Si and CuO, reducing the CuO in high-temperature inert atmosphere, and reacting with silicon to prepare Cu3Si, mixtures of Si with MgO, etc., in which Cu3The amount of Si is very small (Y.Zhang et al, J.alloys Compd.2019, 792, 341-347). Klementov et al prepare Cu by CVD5Si and Cu3Si mixtures were used as electrodes (m.klementov et al, j.cryst.growth.2017, 465, 6-11); woo et al prepared Ge-Cu and Cu by controlled growth using bilayer films3Si mixtures were used as electrodes (J.Woo et al, Crystal. growth Des.2015, 15, 5355-5359); pure phase Cu can not be obtained by the above preparation methods3Si, limiting its further development.
In general, Cu3The use of Si is still under investigation. At present, the country isGeneral internal and external thinking of Cu3Si is a catalytic active phase of organosilicon monomer synthesis reaction (E.Suzuki et al, J.Catal.1990, 125, 390-. But Cu3The Si active phase is formed in situ during the reaction, currently with respect to Cu3The research that Si is directly used for catalyzing the synthesis reaction of the organic silicon monomer is not reported.
At present, the network also discloses that pure aluminum ingots, electrolytic copper and crystalline silicon are used as raw materials to prepare copper-silicon alloy through a direct smelting process, the copper-silicon alloy obtained through the direct smelting process is of a blocky structure and is a mixture, and pure-phase Cu cannot be obtained3Si, which in turn cannot be used in applications such as catalytic organosilicon monomer synthesis.
In view of the foregoing, up to now, there has been a simple production of pure phase Cu3The method for preparing Si has not been reported yet, so that the method for preparing pure-phase Cu has low development cost, is simple and practical and is environment-friendly3The method for preparing Si, especially the large-scale preparation thereof, has important scientific significance and application value.
Disclosure of Invention
Therefore, the invention provides a preparation method and application of the pure-phase copper-silicon alloy material with simple preparation method and low preparation cost.
In order to achieve the purpose, the invention discloses a preparation method of a copper-silicon alloy material, which comprises the following steps:
step 1: uniformly mixing Cu powder and Si powder to obtain a mixture; in the mixture, the mass percentage content of Cu powder is 60-80%, and the rest components are Si powder;
step 2: putting the mixture into a high-temperature furnace, pretreating the mixture in an inert atmosphere, and calcining the mixture at the high temperature of 700-1300 ℃ for 2-10 h to obtain the copper-silicon alloy material Cu3Si。
The invention adopts the dry method environment, selects proper reactant proportion, calcining atmosphere, calcining temperature and calcining time, and obtains the product under the synergistic effect of dynamics and thermodynamicsTo pure phase copper silicon alloy materials. When the mass percentage of the Cu powder in the mixture obtained in the step 1 of the invention is less than 60 percent, the Cu is obtained3The mixture of Si, Si and Cu, Cu powder with the mass percent of more than 80 percent can not obtain Cu3And (3) Si. Therefore, the Cu powder of the present invention has a mass percentage of 60% to 80% as an optimum ratio.
The calcination temperature in step 2 may specifically be: 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, etc., but are not limited to the recited values, and other values not recited within the numerical range are equally applicable. The calcination time is 2 h-10 h, and specifically can be as follows: 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc., but are not limited to the recited values, and other values not recited in the numerical range are also applicable.
Further, the copper powder in the step 1 is one of the following: nano copper powder, micron copper powder, bulk copper powder or metallurgical copper powder.
Further, the silicon powder in the step 1 is one of the following: nano silicon powder, micron silicon powder, metallurgical silicon powder or block silicon powder.
Further, in the step 1, the uniformly mixing the Cu powder and the Si powder includes: and carrying out ball milling, oscillation or grinding on the Cu powder and the Si powder for 10 min-1 h.
Further, in the step 2, the high-temperature furnace includes one of the following: a box-type atmosphere furnace, a vacuum tube furnace, a lifting atmosphere furnace, an atmosphere muffle furnace or an atmosphere resistance furnace.
Further, in the step 2, the inert gas used in the inert atmosphere is one of the following gases: n is a radical of2、Ar、H2Ar or He.
Further, in the step 2, the pretreatment under the inert atmosphere is as follows: and introducing inert gas with the flow rate of 20 mL/min-100 mL/min into the mixture of the Cu powder and the Si powder for 10 min-1 h. For example, the time for introducing the inert gas may be 10min, 20min, 30min, 40min, 50min or 1h, but is not limited to the enumerated values, and other values not enumerated within the range of the enumerated values are also applicable. Meanwhile, the flow rate of the introduced inert gas may be specifically: 20mL/min, 30mL/min, 40mL/min, 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min, or 100mL/min, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
The invention also discloses application of the copper-silicon alloy material, and application of the copper-silicon alloy material as an organic silicon monomer synthesis reaction catalyst.
Further, the copper-silicon alloy material is applied to the selective synthesis of the trimethoxy silane catalyst by the reaction of silicon and methanol.
The invention also discloses a copper-silicon alloy material prepared by the preparation method, wherein the copper-silicon alloy material comprises the components of Cu3And Si, wherein Cu and Si in the copper-silicon alloy material are uniformly dispersed.
Further, the copper-silicon alloy material is in a sheet shape, a coral shape, a flower shape or a block shape; the copper-silicon alloy material is in a sheet shape, a coral shape, a flower shape or a block shape; the copper-silicon alloy material belongs to a submicron material, and the size of the material is 100 nm-1 mu m. For example, the size of the copper-silicon alloy material is 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, or 1 μm, but the copper-silicon alloy material is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable.
Compared with the prior art, the invention has the following beneficial effects:
1. the copper-silicon alloy material (Cu) of the invention3Si), and the copper silicon has good dispersibility, strong interaction between the copper and the silicon, good stability, and is a catalyst and an electrode material with great potential; the copper-silicon alloy material can be used as a catalyst for synthesizing trimethoxy silane.
2. Cu of the invention3According to the preparation method of Si, the product does not need to be purified, only high-temperature calcination is needed, the reactants are cheap and easy to obtain, the process is simple, the repeatability is good, and the preparation method is suitable for industrial production.
3. In terms of catalytic effect, first, Cu prepared by the present invention3Si can be used as a catalytic active phase for preparing trimethoxy silane by a direct method, and can be directly used for catalytic reaction, so that the induction period is shortened; secondly, the original hairPrepared Cu3The active sites of Si are many, and the catalytic performance is good; finally, Cu produced by the invention3Si, copper and silicon are directly bonded, the interaction is strong, the condition that the reduction of active sites caused by Cu precipitation influences the catalytic performance is avoided, and the stability is good. Cu prepared by the invention3Compared with commercial cuprous chloride catalyst, the Si can obviously improve the selectivity and yield of catalytic reaction.
Drawings
FIG. 1 is an XRD pattern of the catalyst described in example 1 of the present invention;
FIG. 2 is an SEM image of a catalyst according to example 1 of the present invention;
FIG. 3 is a HRTEM image of the catalyst of example 1 of the present invention;
FIG. 4 is an SEM image of a catalyst described in example 2 of the present invention;
FIG. 5 is an SEM image of a catalyst described in example 3 of the present invention;
FIG. 6 is an SEM image of a catalyst described in example 4 of the present invention;
FIG. 7 is an SEM image of a catalyst described in example 5 of the present invention.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the technical means in detail, the following detailed description is given with reference to specific embodiments.
Example 1
The embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.2g of nano Cu and 0.8g of metallurgical Si are ball-milled and mixed uniformly, and the mixing time is 10 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into a box type atmosphere furnace, and flowing at 20mL/min inert atmosphere (N)2Atmosphere) for 1h, and calcining at 700 ℃ for 10h to obtain the copper-silicon alloy (Cu)3Si)。
The obtained alloy material was characterized by using an X' Pert PRO MPD type multifunctional X-ray diffractometer manufactured by Panalytical corporation (Pasnay), the Netherlands, and the result is shown in FIG. 1; the obtained alloy material was observed for its internal structure on a transmission electron microscope of JEM-2010F type manufactured by JEOL, Japan, and the result is shown in FIG. 2.
The prepared material is characterized by XRD, and as can be seen from figure 1, all diffraction peaks (marked by ". cndot.") belong to Cu3Characteristic diffraction peak of Si; the prepared material is characterized by SEM, and as can be seen from figure 2, the material is in a flaky aggregate; the prepared material is characterized by HRTEM, and as can be seen from FIG. 3, the catalyst has a sheet structure and a size of about 350 nm.
Example 2:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is coral-shaped.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.3g of nano Cu and 0.7g of metallurgical Si are uniformly mixed in an oscillating way, and the mixing time is 20 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into a box type atmosphere furnace, and flowing at 30mL/min under inert atmosphere (N)2Atmosphere) for 50min, and calcining at 1000 ℃ for 5h to obtain the copper-silicon alloy (Cu)3Si)。
The prepared material was characterized by SEM, and as can be seen from FIG. 4, the catalyst was a coral-like structure.
Example 3:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is in a flower shape.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.4g of nano Cu and 0.6g of metallurgical Si are ball-milled and mixed uniformly, and the mixing time is 20 min;
(2) placing the above mixture into a porcelain boat, spreading into a thin layer, and placing into a box-type atmosphere furnaceUnder an inert atmosphere (N) at a flow rate of 20mL/min2Atmosphere) for 10min, and calcining at 700 ℃ for 2h to obtain the copper-silicon alloy (Cu)3Si)。
The prepared material is characterized by SEM, and as can be seen from figure 5, the catalyst has a flower-like structure.
Example 4:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is in a block shape.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.5g of nano Cu and 0.5g of metallurgical Si are ball-milled and mixed uniformly for 30 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into a box-type atmosphere furnace, and introducing into an inert atmosphere (N) at a flow rate of 40mL/min2Atmosphere) for 30min, and calcining at 700 ℃ for 8h to obtain the copper-silicon alloy (Cu)3Si)。
The prepared material is characterized by SEM, and as can be seen from FIG. 6, the catalyst is in a blocky structure.
Example 5:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is in a block shape.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.6g of nano Cu and 0.4g of metallurgical Si are ball-milled and mixed uniformly for 30 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into a vacuum tube furnace, and introducing into an inert atmosphere (N) at a flow rate of 50mL/min2Atmosphere) for 20min, and calcining at 700 ℃ for 6h to obtain the copper-silicon alloy (Cu)3Si)。
The prepared material is characterized by SEM, and as can be seen from FIG. 7, the catalyst is in a blocky structure.
Example 6:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly mixed in an oscillating manner, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) uniformly mixing 1.2g of nano Cu and 0.8g of nano Si for 10 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into a vacuum tube furnace, and flowing in an inert atmosphere (N) with a flow rate of 60mL/min2Atmosphere) for 210min, and calcining at 700 ℃ for 6h to obtain the copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Example 7:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.2g of nano Cu and 0.8g of micron Si are shaken and mixed evenly, and the mixing time is 40 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into a vacuum tube furnace, and flowing in an inert atmosphere (N) with a flow rate of 60mL/min2Atmosphere) for 20min, and calcining at 700 ℃ for 8h to obtain the copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Example 8:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.2g of nano Cu and 0.8g of block Si are oscillated and mixed uniformly for 40 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into a vacuum tube furnace, and flowing at 70mL/min under inert atmosphere (N)2Atmosphere) for 15min, and calcining at 1200 ℃ for 4h to obtain the copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Example 9:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) grinding and uniformly mixing 1.2g of micron Cu and 0.8g of metallurgical Si for 50 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into an atmosphere muffle furnace, and flowing at 80mL/min under inert atmosphere (N)2Atmosphere) for 15min, and calcining at 1200 ℃ for 4h to obtain the copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Example 10:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.2g of block Cu and 0.8g of metallurgical Si are ground and mixed uniformly, and the mixing time is 50 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into an atmosphere muffle furnace, and flowing at 90mL/min under inert atmosphere (N)2Atmosphere) for 15min, and calcining at 1100 ℃ for 6h to obtain the copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Example 11:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.2g of block Cu and 0.8g of block Si are ground and mixed uniformly for 1 h;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into an atmosphere muffle furnace, pretreating in an inert atmosphere (Ar atmosphere) at a flow rate of 90mL/min for 15min, and calcining at 1000 deg.C for 7h to obtain copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Example 12:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.2g of nano Cu and 0.8g of metallurgical Si are ground and mixed uniformly, and the mixing time is 1 h;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into an atmosphere muffle furnace, pretreating in an inert atmosphere (Ar atmosphere) at a flow rate of 90mL/min for 15min, and calcining at 1000 deg.C for 7h to obtain copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Example 13:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) grinding and uniformly mixing 1.2g of nano Cu and 0.8g of metallurgical Si for 10 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into a lifting atmosphere furnace, pretreating for 10min under inert atmosphere (Ar atmosphere) with flow rate of 100mL/min, and calcining at 1300 deg.C for 2h to obtain copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Example 14:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) grinding and uniformly mixing 1.2g of nano Cu and 0.8g of metallurgical Si for 10 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into an atmosphere resistance furnace, pretreating in an inert atmosphere (He atmosphere) with flow rate of 100mL/min for 10min, and calcining at 900 deg.C for 8h to obtain copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Example 15:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) grinding and uniformly mixing 1.2g of nano Cu and 0.8g of metallurgical Si for 10 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into an atmosphere resistance furnace, pretreating for 30min under inert atmosphere (He atmosphere) with flow rate of 70mL/min, and calcining at 800 deg.C for 9h to obtain copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Example 16:
the embodiment provides a copper-silicon alloy and a preparation method thereof, wherein the copper-silicon alloy contains a Cu element and a Si element, the Cu and the Si in the copper-silicon alloy are uniformly dispersed, and the copper-silicon alloy is flaky.
The preparation method of the copper-silicon alloy comprises the following steps:
(1) 1.2g of metallurgical Cu and 0.8g of metallurgical Si are ground and uniformly mixed, and the mixing time is 10 min;
(2) placing the mixture into a porcelain boat, spreading into a thin layer, placing into an atmosphere resistance furnace, pretreating for 10min under inert atmosphere (He atmosphere) with flow rate of 100mL/min, and calcining at 700 deg.C for 10h to obtain copper-silicon alloy (Cu)3Si)。
And characterizing the prepared material by adopting SEM, wherein the catalyst is of a sheet structure.
Comparative example 1:
this comparative example provides a method of preparation of a silicone blend which differs from example 1 only in that: there is no high temperature calcination of step 2.
The preparation method of the mixture comprises the following steps:
1.2g of nano Cu and 0.8g of metallurgical Si are ball-milled and mixed uniformly, and the mixing time is 10 min.
Comparative example 2:
this comparative example provides a commercial cuprous chloride catalyst, a commercially available product, purchased from south-of-china and austin chemical limited, under the brand name a-6616.
The copper-silicon alloy materials prepared in the embodiments 1 to 16 of the invention can be used as a catalyst for the synthesis reaction of an organic silicon monomer, and can also be used as a catalyst for selectively synthesizing trimethoxy silane by the reaction of silicon and methanol.
The materials prepared in examples 1 to 16 and comparative examples 1 to 2 were used to catalyze the reaction of silicon powder and methanol to prepare trimethoxysilane, to evaluate the catalytic performance of the catalyst. The performance evaluation of the catalyst is carried out by adopting a slurry bed reactor, and the evaluation process is as follows: firstly, adding 400g of organic solvent into a slurry bed reactor, and starting mechanical stirring; secondly, 200g of silicon powder and 2g of catalyst (namely the silicon-copper alloy prepared in each example and the catalyst adopted in comparative example 1-2) are ground to form a fresh contact body; then, the reactor was heated to 220 ℃ to activate for 1 hour, methanol was introduced (methanol flow rate 350. mu.L/min), the product after the reaction was condensed by a condenser tube and collected by a cold trap, and the product was diluted with an organic solvent and then quantitatively analyzed by gas chromatography. Samples were taken for three and twelve hours each to test the instantaneous value of each component, and finally, the average value of each component in the collection bottle was analyzed after twelve hours of reaction, the components including methanol, dimethoxydihydrosilane, trimethoxysilane, methyltrimethoxysilane and tetramethoxysilane.
The results of the tests for the catalytic activity of the catalysts in the above examples and comparative examples and the methanol distribution in the total product are shown in table 1; wherein, the distribution of the products is calculated by the area percentage corresponding to the reaction products in the gas chromatographic analysis result.
Table 1 table of catalyst activity test results
Note: dihydro: dimethoxydihydro-silane; trimethyl: trimethoxysilane; and A, third: methyltrimethoxysilane; tetramethyl: tetramethoxysilane.
As can be seen from Table 1, the catalysts prepared in examples 1-16 have relatively good catalytic activity, fast start-up, good stability, and the selectivity of trimethoxy silane can be continuously maintained above 80%; cu produced by metallurgical Si3The Si activity is higher, which is suitable for preparing Cu on a large scale3Si has great significance; furthermore, it was found that the Cu flakes were more flaky than the flower-like, coral-like, block-like Cu flakes3Si has better catalytic activity; the catalyst prepared in comparative example 1 has no catalytic activity; although the catalyst in comparative example 2 starts up quickly, the stability is not good, and the product is acidic and is not in accordance with the concept of green chemistry.
As can be seen from the average methanol content of the total products, the conversion rate of silicon powder is higher in examples 1-16; however, the silicon powder in comparative example 1 is not substantially converted, because the purpose of generating the copper-silicon alloy can not be achieved without the treatment of high-temperature calcination, and the catalytic reaction is not performed; comparative example 2 did not reach a desirable level of catalytic activity.
The results of the above examples and comparative examples show that the catalysts prepared according to the present invention have significant advantages in terms of catalytic performance, due to the following: first, Cu3Si is a catalytic active phase for preparing trimethoxy silane by a direct method, and Cu prepared by the method3Si can be directly used for catalytic reaction, so that the induction period is shortened; secondly, Cu prepared by the invention3The active sites of Si are many, and the catalytic performance is good; finally, Cu produced by the invention3Si, copper and silicon are directly bonded, the interaction is strong, the reduction of active sites caused by Cu precipitation does not exist, the catalytic performance is influenced, and the stability is good.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein or by using equivalent structures or equivalent processes performed in the present specification, and are included in the scope of the present invention.
Claims (9)
1. A preparation method of a copper-silicon alloy material is characterized by comprising the following steps:
step 1: uniformly mixing Cu powder and Si powder to obtain a mixture; in the mixture, the mass percentage content of Cu powder is 60-80%;
step 2: putting the mixture into a high-temperature furnace, pretreating the mixture in an inert atmosphere, and calcining the mixture at the high temperature of 700-1300 ℃ for 2-10 h to obtain the copper-silicon alloy material Cu3Si。
2. The method for preparing a copper-silicon alloy material according to claim 1, wherein the copper powder in the step 1 is one of the following: nano copper powder, micron copper powder, bulk copper powder or metallurgical copper powder.
3. The method for preparing the copper-silicon alloy material according to claim 1, wherein the silicon powder in the step 1 is one of the following: nano silicon powder, micron silicon powder, metallurgical silicon powder or block silicon powder.
4. The method for preparing the copper-silicon alloy material according to claim 1, wherein in the step 1, the uniformly mixing the Cu powder and the Si powder comprises: and carrying out ball milling, oscillation or grinding on the Cu powder and the Si powder for 10 min-1 h.
5. The method for preparing the copper-silicon alloy material according to claim 1, wherein the pretreatment in the step 2 under the inert atmosphere is: and introducing inert gas with the flow rate of 20 mL/min-100 mL/min into the mixture of the Cu powder and the Si powder for 10 min-1 h.
6. Use of a copper silicon alloy material according to any one of claims 1 to 5, characterized in that: the copper-silicon alloy material is applied as an organic silicon monomer synthesis reaction catalyst.
7. Use of a copper silicon alloy material according to claim 6, characterized in that: the copper-silicon alloy material is applied to the selective synthesis of the trimethoxy silane catalyst by the reaction of silicon and methanol.
8. The copper-silicon alloy material produced by the production method according to any one of claims 1 to 5, characterized in that: the copper-silicon alloy material comprises Cu3And Si, wherein Cu and Si in the copper-silicon alloy material are uniformly dispersed.
9. The copper-silicon alloy material prepared by the preparation method according to claim 8, wherein: the copper-silicon alloy material is in a sheet shape, a coral shape, a flower shape or a block shape; the copper-silicon alloy material belongs to a submicron material, and the size of the material is 100 nm-1 mu m.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB900123A (en) * | 1959-01-26 | 1962-07-04 | Goldschmidt Ag Th | Improvements in or relating to the production of alkyl-or aryl-halosilanes |
| EP0567867A2 (en) * | 1992-04-30 | 1993-11-03 | International Business Machines Corporation | Oxidation-resistant compound of Cu3Si and fabrication thereof |
| US6046108A (en) * | 1999-06-25 | 2000-04-04 | Taiwan Semiconductor Manufacturing Company | Method for selective growth of Cu3 Ge or Cu5 Si for passivation of damascene copper structures and device manufactured thereby |
| CN101671355A (en) * | 2009-09-30 | 2010-03-17 | 哈尔滨工业大学 | Method for compositing trialkoxysilanes by adopting multistage fluidized bed |
| CN101818048A (en) * | 2010-01-21 | 2010-09-01 | 中南大学 | Method for preparing copper silicon alloy modified carbon/ceramic friction material |
| CN102962434A (en) * | 2012-10-31 | 2013-03-13 | 西安交通大学 | Silicon carbide/copper silicon alloy codual-continuous composite and preparation method thereof |
| CN105541337A (en) * | 2015-12-25 | 2016-05-04 | 中国科学院上海硅酸盐研究所 | Multi-metal silicide powder and preparing method thereof |
| CN105944722A (en) * | 2016-05-18 | 2016-09-21 | 中国科学院过程工程研究所 | Cu-Cu2O-CuO ternary copper catalyst and preparation method and application thereof |
-
2020
- 2020-10-27 CN CN202011164330.6A patent/CN112342422A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB900123A (en) * | 1959-01-26 | 1962-07-04 | Goldschmidt Ag Th | Improvements in or relating to the production of alkyl-or aryl-halosilanes |
| EP0567867A2 (en) * | 1992-04-30 | 1993-11-03 | International Business Machines Corporation | Oxidation-resistant compound of Cu3Si and fabrication thereof |
| US6046108A (en) * | 1999-06-25 | 2000-04-04 | Taiwan Semiconductor Manufacturing Company | Method for selective growth of Cu3 Ge or Cu5 Si for passivation of damascene copper structures and device manufactured thereby |
| CN101671355A (en) * | 2009-09-30 | 2010-03-17 | 哈尔滨工业大学 | Method for compositing trialkoxysilanes by adopting multistage fluidized bed |
| CN101818048A (en) * | 2010-01-21 | 2010-09-01 | 中南大学 | Method for preparing copper silicon alloy modified carbon/ceramic friction material |
| CN102962434A (en) * | 2012-10-31 | 2013-03-13 | 西安交通大学 | Silicon carbide/copper silicon alloy codual-continuous composite and preparation method thereof |
| CN105541337A (en) * | 2015-12-25 | 2016-05-04 | 中国科学院上海硅酸盐研究所 | Multi-metal silicide powder and preparing method thereof |
| CN105944722A (en) * | 2016-05-18 | 2016-09-21 | 中国科学院过程工程研究所 | Cu-Cu2O-CuO ternary copper catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| HUI CAI ET AL.: "Reactive synthesis of porous Cu3Si compound", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 张鉴: "《冶金熔体和溶液的计算热力学》", 31 March 2007, 冶金工业出版社 * |
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