CN118106011A - Amorphous copper composite material and preparation method and application thereof - Google Patents
Amorphous copper composite material and preparation method and application thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 97
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 92
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001879 copper Chemical class 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000012266 salt solution Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 22
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000011941 photocatalyst Substances 0.000 claims abstract description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 9
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002905 metal composite material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010668 complexation reaction Methods 0.000 abstract 1
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- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000000843 powder Substances 0.000 description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000007605 air drying Methods 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
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- 231100000719 pollutant Toxicity 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
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- 239000005751 Copper oxide Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 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 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- LLOSLLNFDURHEB-UHFFFAOYSA-L dichlorocobalt pentahydrate Chemical compound O.O.O.O.O.[Cl-].[Cl-].[Co++] LLOSLLNFDURHEB-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000013079 quasicrystal Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen 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
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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
- 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
- B01J35/39—Photocatalytic properties
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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
- 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
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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
- 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
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Abstract
Description
技术领域Technical Field
本发明属于非晶态铜技术领域，具体涉及一种非晶态铜复合材料及其制备方法和应用。The invention belongs to the technical field of amorphous copper, and in particular relates to an amorphous copper composite material and a preparation method and application thereof.
背景技术Background technique
非晶态金属是指在原子尺度上结构无序的一种金属材料。大部分金属材料具有很高的有序结构，原子呈现周期性排列(晶体)，表现为平移对称性，或者是旋转对称，镜面对称，角对称(准晶体)等。而与此相反，非晶态金属不具有任何的长程有序结构，但具有短程有序和中程有序。一般地，具有这种无序结构的非晶态金属可以从其液体状态直接冷却得到，故又称为"玻璃态"。所以，非晶态金属又称为"金属玻璃"、"玻璃态金属"、"液态金属"或“大块金属玻璃”。非晶态的基本特征是其构成的原子或分子在很大程度上的排列混乱，体系的自由能比对应的晶态要高，是一种热力学意义上的亚稳态。Amorphous metal refers to a metal material with disordered structure at the atomic scale. Most metal materials have a highly ordered structure, with atoms arranged periodically (crystals), showing translational symmetry, or rotational symmetry, mirror symmetry, angular symmetry (quasicrystals), etc. In contrast, amorphous metals do not have any long-range ordered structure, but have short-range order and medium-range order. Generally, amorphous metals with such disordered structures can be directly cooled from their liquid state, so they are also called "glassy state". Therefore, amorphous metals are also called "metallic glass", "glassy metal", "liquid metal" or "bulk metallic glass". The basic characteristic of the amorphous state is that the atoms or molecules that constitute it are arranged in a disordered manner to a large extent, and the free energy of the system is higher than that of the corresponding crystalline state. It is a metastable state in the thermodynamic sense.
非晶材料的结构特点：Structural characteristics of amorphous materials:
(1)结构长程无序：晶体结构的特点是其点阵周期性。非晶态材料则是一种无序结构，其原子排列不再具有长程周期性，如“晶格点”、“晶格常数”、“晶粒”等概念都失去了固有意义。(1) Long-range structural disorder: The characteristic of crystal structure is its lattice periodicity. Amorphous materials are a disordered structure whose atomic arrangement no longer has long-range periodicity. Concepts such as "lattice point", "lattice constant" and "grain" have lost their inherent meaning.
(2)短程有序：在非晶态材料中，最近邻原子间距与晶体的差距很小，配位数也很相近，但是在次近邻原子的关系上就可能有显著的差别。(2) Short-range order: In amorphous materials, the distance between the nearest neighbor atoms is very small compared to that in the crystal, and the coordination numbers are also very similar, but there may be significant differences in the relationship between the next nearest neighbor atoms.
(3)结构均匀：没有像晶体的结构缺陷，如晶界、孪晶、晶格缺陷、错位、层错等。(3) Uniform structure: There are no structural defects like crystals, such as grain boundaries, twins, lattice defects, dislocations, stacking faults, etc.
(4)成分均匀：在非晶态形成的过程中，无晶体的析出物、偏析以及其它成分变化。(4) Uniform composition: During the formation of the amorphous state, there are no crystalline precipitates, segregation, or other composition changes.
(5)结构处于热力学上的非平衡态，总有进一步转变为稳定晶态的倾向。(5) The structure is in a thermodynamically non-equilibrium state and always tends to further transform into a stable crystalline state.
无定形的结构使非晶态金属具有许多比普通晶态金属优异的性能。根据非晶态材料优良的化学性能、光学性能、半导体性能等可广泛应用于不同领域。The amorphous structure makes amorphous metals have many superior properties than ordinary crystalline metals. Based on the excellent chemical properties, optical properties, semiconductor properties, etc. of amorphous materials, they can be widely used in different fields.
抗腐蚀性：由于没有晶粒及其缝隙，非晶态金属材料具有优良的耐腐蚀性。Corrosion resistance: Due to the absence of grains and their gaps, amorphous metal materials have excellent corrosion resistance.
催化电极材料：非晶态金属可以做出性能优异的催化电极材料。Catalytic electrode materials: Amorphous metals can be used to make catalytic electrode materials with excellent performance.
氢催化材料：非晶态金属可以制成催化加氢、催化脱氢的电极材料；在石油工业中，加氢会使分子链缩短，以便制取轻质油；脱氢会使分子链增长，以便制取大分子材料。Hydrogen catalytic materials: Amorphous metals can be made into electrode materials for catalytic hydrogenation and catalytic dehydrogenation. In the petroleum industry, hydrogenation shortens the molecular chain to produce light oil; dehydrogenation lengthens the molecular chain to produce macromolecular materials.
有些非晶态金属，其原子特殊电子状态有利于吸收太阳能并激发出电子，这就是做成太阳能电池的好材料。Some amorphous metals have special electronic states of their atoms that are conducive to absorbing solar energy and exciting electrons, making them good materials for making solar cells.
制备非晶态金属的方法包括：物理气相沉积、固相烧结法、离子辐射法、甩带法(连续铸造法其中一种)和机械法。制备非晶态金属的关键问题：第一，必须形成原子(分子)混乱排列的状态-非晶态；第二，将热力学上的非平衡态保存下来，而不向晶态转变。非晶态材料制备原理示意图见图1。Methods for preparing amorphous metals include: physical vapor deposition, solid phase sintering, ion radiation, belt spinning (one of the continuous casting methods) and mechanical methods. The key issues in preparing amorphous metals are: first, a state of chaotic arrangement of atoms (molecules) must be formed - amorphous state; second, the thermodynamic non-equilibrium state must be preserved without transforming into a crystalline state. The schematic diagram of the principle of preparing amorphous materials is shown in Figure 1.
产生非晶态金属的技术关键之一，就是如何快速冷却的问题；不同的物质形成非晶态所需要的冷却速度大不相同。例如，普通的玻璃只要慢慢冷却下来，得到的玻璃就是非晶态的。而单一的金属则需要每秒高达一亿度以上的冷却速度才能形成非晶态，非晶态金属材料难以制备。因此，急需开发出一种制备非晶态金属材料的方法。One of the key technologies to produce amorphous metals is how to cool them quickly. Different materials require very different cooling speeds to form amorphous. For example, ordinary glass will be amorphous as long as it is slowly cooled. However, a single metal requires a cooling speed of more than 100 million degrees per second to form an amorphous state. Amorphous metal materials are difficult to prepare. Therefore, it is urgent to develop a method for preparing amorphous metal materials.
发明内容Summary of the invention
本发明提供了一种非晶态铜复合材料及其制备方法和应用，解决了现有技术难以制备出非晶态金属材料的问题。The invention provides an amorphous copper composite material and a preparation method and application thereof, which solves the problem that it is difficult to prepare amorphous metal materials in the prior art.
一种非晶态铜复合材料的制备方法，具体包括以下步骤：A method for preparing an amorphous copper composite material comprises the following steps:
制备铜盐溶液；preparing a copper salt solution;
向铜盐溶液中加入氮化碳前驱体，混合均匀后干燥得到混合物；其中，铜盐和氮化碳前驱体的摩尔质量比为1:8～4；Adding a carbon nitride precursor to a copper salt solution, mixing evenly and drying to obtain a mixture; wherein the molar mass ratio of the copper salt to the carbon nitride precursor is 1:8-4;
将混合物在350～450℃反应2～4h，得所述非晶态铜复合材料。The mixture is reacted at 350-450° C. for 2-4 hours to obtain the amorphous copper composite material.
优选的，所述铜盐为五水合硫酸铜、一水合乙酸铜、氯化铜中的一种或几种。Preferably, the copper salt is one or more of copper sulfate pentahydrate, copper acetate monohydrate, and copper chloride.
优选的，所述氮化碳前驱体为尿素、三聚氰胺、双氰胺中的一种或几种。Preferably, the carbon nitride precursor is one or more of urea, melamine and dicyandiamide.
优选的，所述混合物先用锡纸包裹，然后在350～450℃反应2～4h。Preferably, the mixture is first wrapped with tin foil and then reacted at 350-450° C. for 2-4 hours.
优选的，所述混合物先用锡纸包裹，然后在400℃反应3h，得所述非晶态铜复合材料。Preferably, the mixture is first wrapped with tin foil and then reacted at 400° C. for 3 hours to obtain the amorphous copper composite material.
优选的，所述混合物以速率为2～10℃/min升温至350～450℃。Preferably, the mixture is heated to 350-450° C. at a rate of 2-10° C./min.
优选的，所述铜盐溶液的制备方法为：将铜盐与水混合均匀，得所述铜盐溶液；其中，铜盐与水按比例为0.01mol:40～60mL。Preferably, the copper salt solution is prepared by uniformly mixing copper salt and water to obtain the copper salt solution; wherein the ratio of copper salt to water is 0.01 mol:40-60 mL.
优选的，制备混合物时所述干燥条件为60～80℃下烘烤24～36h。Preferably, when preparing the mixture, the drying condition is baking at 60-80° C. for 24-36 hours.
本发明的第二个目的在于保护所述任一项制备方法制得的非晶态铜复合材料。The second object of the present invention is to protect the amorphous copper composite material prepared by any one of the preparation methods.
本发明的第三个目的在于保护所述的非晶态铜复合材料在制备光催化剂、单原子催化剂、多金属复合材料或氮化碳材料改性中的应用。The third object of the present invention is to protect the use of the amorphous copper composite material in the preparation of photocatalysts, single-atom catalysts, multi-metal composite materials or carbon nitride material modification.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the present invention has the following beneficial effects:
1.为了获得非晶态的金属，一般将金属与其它物质混合后形成。由于原子的种类增多，金属在液体或溶融状态时原子更加难以移动，在冷却时更加难以整齐排列，更容易被“冻结”成非晶。本发明正是利用这一原理，首次在较低的温度下使用一步热缩聚法成功制备了非晶态铜复合材料，填补了该领域的研究空白。本发明利用三聚氰胺、尿素、双氰胺中具有丰富孤对电子的吡啶氮可以与水溶液中的铜离子发生络合作用形成稳定的络合物，将该络合物干燥后通过简便的热缩聚法可制备一种碳氮基非晶态铜复合材料，因为热缩聚过程中丰富的吡啶N为金属铜离子提供大量的配位点。最终制得的非晶态铜复合材料可用于制备铜基单原子催化剂、光催化剂等，构筑高效的非均相催化剂。1. In order to obtain an amorphous metal, the metal is generally mixed with other substances to form it. Due to the increase in the types of atoms, it is more difficult for the metal atoms to move when it is in a liquid or molten state, and it is more difficult to arrange them neatly when cooling, and it is easier to be "frozen" into an amorphous state. The present invention uses this principle to successfully prepare an amorphous copper composite material using a one-step thermal polycondensation method at a relatively low temperature for the first time, filling the research gap in this field. The present invention utilizes pyridine nitrogen with abundant lone pair electrons in melamine, urea, and dicyandiamide to form a stable complex with copper ions in an aqueous solution. After the complex is dried, a carbon-nitrogen-based amorphous copper composite material can be prepared by a simple thermal polycondensation method, because the abundant pyridine N in the thermal polycondensation process provides a large number of coordination sites for metal copper ions. The amorphous copper composite material finally obtained can be used to prepare copper-based single-atom catalysts, photocatalysts, etc., to construct efficient heterogeneous catalysts.
2.本发明制备的非晶态铜复合材料中铜非晶态形式稳定存在。2. The amorphous copper composite material prepared by the present invention exists in a stable amorphous copper form.
3.本发明制备的非晶态铜复合材料的比表面积得到显著提高，远远高于同类型过渡金属掺杂氮化碳复合材料；3. The specific surface area of the amorphous copper composite material prepared by the present invention is significantly improved, which is much higher than that of the same type of transition metal-doped carbon nitride composite material;
4.本发明制备的非晶态铜复合材料作为含铜非均相催化剂的中间体使用，不仅能够稳定保持非晶态铜的特性，且以一价和二价的混合价态存在，可为非晶态金属相关催化剂的制备提供新途径。4. The amorphous copper composite material prepared by the present invention is used as an intermediate of a copper-containing heterogeneous catalyst. It can not only stably maintain the characteristics of amorphous copper, but also exist in a mixed valence state of monovalent and divalent copper, which can provide a new way for the preparation of amorphous metal-related catalysts.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为非晶态材料制备原理示意图；FIG1 is a schematic diagram of the preparation principle of amorphous materials;
图2为铜盐与聚合物比例变化对上清液颜色的影响；FIG2 shows the effect of the ratio of copper salt to polymer on the color of the supernatant;
图3为铜盐和三聚氰胺不同比例下复合材料的中铜晶态变化；FIG3 shows the change of the copper crystal state of the composite material at different ratios of copper salt and melamine;
图4为本发明实施例1制备的非晶态铜复合材料的实物图；FIG4 is a physical picture of the amorphous copper composite material prepared in Example 1 of the present invention;
图5为本发明实施例1制备的非晶态铜复合材料的XRD图；FIG5 is an XRD diagram of the amorphous copper composite material prepared in Example 1 of the present invention;
图6为本发明实施例1制备的非晶态铜复合材料的SEM图；FIG6 is a SEM image of the amorphous copper composite material prepared in Example 1 of the present invention;
图7为本发明实施例1制备的非晶态铜复合材料的TEM图；FIG7 is a TEM image of the amorphous copper composite material prepared in Example 1 of the present invention;
图8为本发明实施例1制备的非晶态铜复合材料的HRTEM图；FIG8 is a HRTEM image of the amorphous copper composite material prepared in Example 1 of the present invention;
图9为本发明实施例1制备的非晶态铜复合材料的EDS图；FIG9 is an EDS image of the amorphous copper composite material prepared in Example 1 of the present invention;
图10为本发明实施例1制备的非晶态铜复合材料的XPS图；FIG10 is an XPS graph of the amorphous copper composite material prepared in Example 1 of the present invention;
图11为本发明对比例1中将铜盐溶液与三聚氰胺混合后分层图；FIG11 is a diagram showing the layers after mixing the copper salt solution and melamine in Comparative Example 1 of the present invention;
图12为本发明对比例3和对比例4制备的晶态铜复合材料的XRD图；FIG12 is an XRD diagram of the crystalline copper composite materials prepared in Comparative Examples 3 and 4 of the present invention;
图13为本发明对比例5和对比例6制备的晶态铜复合材料的XRD图；FIG13 is an XRD diagram of the crystalline copper composite materials prepared in Comparative Examples 5 and 6 of the present invention;
图14为本发明对比例5制备的复合材料的SEM(a)和TEM(b)图；FIG14 is a SEM (a) and TEM (b) image of the composite material prepared in Comparative Example 5 of the present invention;
图15为本发明应用例(1)中制备的非晶态亚铜掺杂氮化碳非均相催化剂的降解效果；FIG15 shows the degradation effect of the amorphous cuprous carbon nitride-doped heterogeneous catalyst prepared in Application Example (1) of the present invention;
图16为本发明应用例(2)中制备的氮化碳负载单原子铜催化剂的SEM(a)和TEM(b)；FIG16 is a SEM (a) and TEM (b) of the carbon nitride-supported single-atom copper catalyst prepared in Application Example (2) of the present invention;
图17为本发明应用例(2)中制备的氮化碳负载单原子铜催化剂活化H2O2和PMS降解污染物时，初始pH对催化剂催化性能的影响；FIG. 17 shows the effect of the initial pH on the catalytic performance of the catalyst when the carbon nitride-supported single-atom copper catalyst prepared in Application Example (2) of the present invention activates H 2 O 2 and PMS to degrade pollutants;
图18为本发明应用例(3)中制备的Cu、Co共掺杂氮化碳复合催化剂活化H2O2降解污染物图。FIG. 18 is a diagram showing the activation of H 2 O 2 to degrade pollutants by the Cu and Co co-doped carbon nitride composite catalyst prepared in Application Example (3) of the present invention.
具体实施方式Detailed ways
下面将结合本发明具体实施，对本发明中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the present invention will be described clearly and completely below in conjunction with the specific implementation of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
本发明各实施例中所述方法，如无特殊说明，均为常规方法。所用的材料、试剂等，如无特殊说明，均可从商业途径得到。The methods described in the embodiments of the present invention are conventional methods unless otherwise specified. The materials, reagents, etc. used can be obtained from commercial sources unless otherwise specified.
三聚氰胺、尿素、双氰胺分子中含有孤对电子的吡啶氮物种能够与金属离子发生配位络合作用，形成一种稳定的含铜络合物。硫酸铜、乙酸铜、氯化铜是最常见的铜盐，在水溶液中有较大的溶解度，避免使用其它溶剂增加制备成本。首先，在水中添加铜盐使其完全溶解制备铜盐溶液。其次，在铜盐溶液中添加氮化碳前驱体搅拌使其混合均匀，达到预组装目的，其中，铜盐和聚合物的摩尔质量比1:8～1:4，因为铜盐过量一方面会造成材料的浪费，络合物沉淀后铜离子过剩会使上清液会有铜离子颜色，见图2；另一方面，过量的铜盐会使最终复合材料中混有铜的氧化物，无法保证非晶态铜复合材料的纯度；图3为铜盐和三聚氰胺不同比例下复合材料的中铜晶态变化。第三，将混合均匀的络合物在60℃下烘干，研磨得到淡蓝色粉末，即为含铜络合物。第四，将含铜络合物转移至具盖坩埚中，并用锡纸包裹密闭，是为了降低挥发，提高复合材料的产量，在350～450℃下煅烧2～4小时，即可得到蓬松的墨绿色非晶态铜复合材料，如图4所示。The pyridine nitrogen species containing lone pairs of electrons in melamine, urea, and dicyandiamide molecules can coordinate and complex with metal ions to form a stable copper-containing complex. Copper sulfate, copper acetate, and copper chloride are the most common copper salts, which have a large solubility in aqueous solution, avoiding the use of other solvents to increase the preparation cost. First, copper salt is added to water to completely dissolve it to prepare a copper salt solution. Secondly, a carbon nitride precursor is added to the copper salt solution and stirred to mix it evenly to achieve the purpose of pre-assembly, wherein the molar mass ratio of copper salt to polymer is 1:8 to 1:4, because excessive copper salt will cause waste of materials on the one hand, and excess copper ions after the complex is precipitated will cause the supernatant to have copper ion color, as shown in Figure 2; on the other hand, excessive copper salt will cause copper oxides to be mixed in the final composite material, and the purity of the amorphous copper composite material cannot be guaranteed; Figure 3 shows the changes in the copper crystal state of the composite material under different proportions of copper salt and melamine. Third, the mixed complex is dried at 60°C and ground to obtain a light blue powder, which is a copper-containing complex. Fourth, the copper-containing complex is transferred to a covered crucible and wrapped with tin foil to reduce volatilization and increase the yield of the composite material. After calcination at 350-450°C for 2-4 hours, a fluffy dark green amorphous copper composite material can be obtained, as shown in Figure 4.
实施例1Example 1
在烧杯中加入40mL去离子水，称取0.01mol五水合硫酸铜加入到烧杯中，室温下磁力搅拌至完全溶解即得铜盐溶液。Add 40 mL of deionized water into a beaker, weigh 0.01 mol of copper sulfate pentahydrate and add it into the beaker, and stir magnetically at room temperature until it is completely dissolved to obtain a copper salt solution.
向铜盐溶液中加入尿素，在室温下继续搅拌30min，至形成完全混合均匀的半固态浆料，然后在鼓风干燥箱中于60℃下烘24h，使去离子水完全挥发，得到淡蓝色混合物；其中，五水合硫酸铜和尿素的摩尔质量比为1:8。Urea was added to the copper salt solution, and stirring was continued at room temperature for 30 minutes to form a completely mixed semi-solid slurry, and then the slurry was dried in a forced air drying oven at 60°C for 24 hours to completely evaporate the deionized water to obtain a light blue mixture; wherein the molar mass ratio of copper sulfate pentahydrate to urea was 1:8.
将淡蓝色混合物研磨成1微米的粉体，放入坩埚，并用锡纸包裹密闭后，转移到带盖氧化铝坩埚中，然后置于管式炉中，在空气氛围下，以2℃/min的升温速率下升温350℃，反应2h，自然冷却后取出研磨，得到墨绿色所述非晶态铜复合材料。The light blue mixture was ground into a 1-micron powder, put into a crucible, and sealed with tin foil, then transferred to an alumina crucible with a lid, and then placed in a tube furnace. In an air atmosphere, the temperature was increased to 350°C at a heating rate of 2°C/min, and the reaction was carried out for 2 hours. After natural cooling, the mixture was taken out and ground to obtain the dark green amorphous copper composite material.
实施例2Example 2
在烧杯中加入40mL去离子水，称取0.01mol一水合乙酸铜加入到烧杯中，室温下磁力搅拌至完全溶解即得铜盐溶液。Add 40 mL of deionized water into a beaker, weigh 0.01 mol of copper acetate monohydrate and add it into the beaker, and stir magnetically at room temperature until it is completely dissolved to obtain a copper salt solution.
向铜盐溶液中加入三聚氰胺，在室温下继续磁力搅拌30min，至形成完全混合均匀的半固态浆料，然后在在鼓风干燥箱中于60℃下烘28h，使去离子水完全挥发，得到淡蓝色混合物；其中，一水合乙酸铜和三聚氰胺的摩尔质量比为1:7。Melamine was added to the copper salt solution, and magnetic stirring was continued at room temperature for 30 minutes to form a completely mixed and uniform semi-solid slurry, and then it was dried in a forced air drying oven at 60°C for 28 hours to completely evaporate the deionized water to obtain a light blue mixture; wherein the molar mass ratio of cupric acetate monohydrate to melamine was 1:7.
将淡蓝色混合物研磨成3微米，放入坩埚，并用锡纸包裹密闭后，转移到带盖氧化铝坩埚中，然后置于管式炉中，在空气氛围下，以4℃/min的升温速率下升温350℃，反应2h，自然冷却后取出研磨得到墨绿色所述非晶态铜复合材料。The light blue mixture was ground into 3 microns, put into a crucible, and sealed with tin foil, then transferred to an alumina crucible with a lid, and then placed in a tube furnace. In an air atmosphere, the temperature was increased to 350°C at a heating rate of 4°C/min, and the reaction was carried out for 2 hours. After natural cooling, the mixture was taken out and ground to obtain the dark green amorphous copper composite material.
实施例3Example 3
在烧杯中加入50mL去离子水，称取0.01mol氯化铜加入到烧杯中，室温下机械搅拌至完全溶解即得铜盐溶液。Add 50 mL of deionized water into a beaker, weigh 0.01 mol of copper chloride and add it into the beaker, and mechanically stir at room temperature until it is completely dissolved to obtain a copper salt solution.
向铜盐溶液中加入双氰胺，在室温下继续机械搅拌40min，至形成完全混合均匀的半固态浆料，然后在在鼓风干燥箱中于70℃下烘32h，使去离子水完全挥发，得到淡蓝色混合物；其中，氯化铜和双氰胺的摩尔质量比为1:6。Dicyandiamide was added to the copper salt solution, and mechanical stirring was continued at room temperature for 40 minutes to form a completely mixed and uniform semi-solid slurry, and then dried in a forced air drying oven at 70°C for 32 hours to completely evaporate the deionized water to obtain a light blue mixture; wherein the molar mass ratio of copper chloride to dicyandiamide was 1:6.
将淡蓝色混合物研磨成6微米粉体，放入坩埚，并用锡纸包裹密闭后，转移到带盖氧化铝坩埚中，然后置于管式炉中，在空气氛围下，以7℃/min的升温速率下升温400℃，反应3h，自然冷却后取出研磨得到墨绿色所述非晶态铜复合材料。The light blue mixture was ground into 6-micron powder, put into a crucible, and sealed with tin foil, then transferred to an alumina crucible with a lid, and then placed in a tube furnace. In an air atmosphere, the temperature was increased to 400°C at a heating rate of 7°C/min, and the reaction was carried out for 3 hours. After natural cooling, the powder was taken out and ground to obtain the dark green amorphous copper composite material.
实施例4Example 4
在烧杯中加入60mL去离子水，称取0.01mol氯化铜加入到烧杯中，室温下机械搅拌至完全溶解即得铜盐溶液。Add 60 mL of deionized water into a beaker, weigh 0.01 mol of copper chloride and add it into the beaker, and stir mechanically at room temperature until it is completely dissolved to obtain a copper salt solution.
向铜盐溶液中加入尿素，在室温下继续机械搅拌60min，至形成完全混合均匀的半固态浆料，然后在在鼓风干燥箱中于80℃下烘36h，使去离子水完全挥发，得到淡蓝色混合物；其中，氯化铜和尿素的摩尔质量比为1:4。Urea was added to the copper salt solution, and mechanical stirring was continued at room temperature for 60 minutes to form a completely mixed and uniform semi-solid slurry, and then dried in a forced air drying oven at 80°C for 36 hours to completely evaporate the deionized water to obtain a light blue mixture; wherein the molar mass ratio of copper chloride to urea was 1:4.
将淡蓝色混合物研磨成10微米粉体，放入坩埚，并用锡纸包裹密闭后，转移到带盖氧化铝坩埚中，然后置于管式炉中，在空气氛围下，以10℃/min的升温速率下升温450℃，反应4h，自然冷却后取出研磨得到墨绿色所述非晶态铜复合材料。The light blue mixture was ground into 10-micron powder, put into a crucible, and sealed with tin foil, then transferred to an alumina crucible with a lid, and then placed in a tube furnace. In an air atmosphere, the temperature was increased to 450°C at a heating rate of 10°C/min, and the reaction was carried out for 4 hours. After natural cooling, the powder was taken out and ground to obtain the dark green amorphous copper composite material.
本发明实施例2～4制备的非晶态铜复合材料与实施例1制备的非晶态铜复合材料的XRD图、SEM图、TEM图、HRTEM图、EDS图、XPS图基本一致，以下仅以实施例1制备的非晶态铜复合材料进行测试。The XRD patterns, SEM patterns, TEM patterns, HRTEM patterns, EDS patterns, and XPS patterns of the amorphous copper composite materials prepared in Examples 2 to 4 of the present invention are substantially consistent with those of the amorphous copper composite materials prepared in Example 1. Only the amorphous copper composite materials prepared in Example 1 are tested below.
图4为本发明实施例1制备的非晶态铜复合材料的实物图。FIG. 4 is a physical picture of the amorphous copper composite material prepared in Example 1 of the present invention.
图5为本发明实施例1制备的非晶态铜复合材料的XRD图(a)，(b)为局部放大图。由图可以看出，非晶态铜复合材料在27°左右处仅有一个晶胞，未观察到任何晶态铜相关的特征峰，证明中间体中铜为非晶态。图6为本发明实施例1制备的非晶态铜复合材料的SEM图。由图中可以看出，非晶态铜复合材料均是由片状结构插层而形成的块体，颗粒尺寸在微米级，表面具有较多镂空结构。图7为本发明实施例1制备的非晶态铜复合材料的TEM图。由图中可以看出，非晶态铜复合材料具有明显的孔洞结构。图8为本发明实施例1制备的非晶态铜复合材料的HRTEM图。由图中可以看出，非晶态铜复合材料的片状插层结构的局部特征，具有蠕虫状的多孔结构，铜为非晶态。图9为本发明实施例1制备的非晶态铜复合材料的EDS图。由图可以看出，非晶态铜复合材料由C、N、Cu和O四种元素组成，其中Cu成功的掺入复合材料中且均匀分布。图10为本发明实施例1制备的非晶态铜复合材料的XPS图。survey谱图结果表明Cu成功的掺入复合材料中，Cu2p证明铜以Cu(I)和Cu(II)两种价态形式存在于复合材料中。Figure 5 is an XRD diagram (a) of the amorphous copper composite material prepared in Example 1 of the present invention, and (b) is a local enlarged diagram. It can be seen from the figure that the amorphous copper composite material has only one unit cell at about 27°, and no characteristic peaks related to crystalline copper are observed, proving that the copper in the intermediate is amorphous. Figure 6 is an SEM image of the amorphous copper composite material prepared in Example 1 of the present invention. It can be seen from the figure that the amorphous copper composite materials are all blocks formed by intercalation of sheet structures, the particle size is in the micron level, and the surface has more hollow structures. Figure 7 is a TEM image of the amorphous copper composite material prepared in Example 1 of the present invention. It can be seen from the figure that the amorphous copper composite material has a clear hole structure. Figure 8 is an HRTEM image of the amorphous copper composite material prepared in Example 1 of the present invention. It can be seen from the figure that the local characteristics of the sheet intercalation structure of the amorphous copper composite material have a worm-like porous structure, and the copper is amorphous. Figure 9 is an EDS image of the amorphous copper composite material prepared in Example 1 of the present invention. As can be seen from the figure, the amorphous copper composite material is composed of four elements: C, N, Cu and O, among which Cu is successfully incorporated into the composite material and evenly distributed. Figure 10 is an XPS graph of the amorphous copper composite material prepared in Example 1 of the present invention. The survey spectrum results show that Cu is successfully incorporated into the composite material, and Cu2p proves that copper exists in the composite material in two valence states, Cu(I) and Cu(II).
对比例1(选取本发明范围以外的铜盐)Comparative Example 1 (Selecting copper salts outside the scope of the present invention)
在烧杯中加入60mL去离子水，称取0.01mol三水合硝酸铜加入到烧杯中，室温下机械搅拌至完全溶解即得铜盐溶液。Add 60 mL of deionized water into a beaker, weigh 0.01 mol of copper nitrate trihydrate and add it into the beaker, and mechanically stir at room temperature until it is completely dissolved to obtain a copper salt solution.
向铜盐溶液中加入三聚氰胺，在室温下继续机械搅拌10min，至形成完全混合均匀的浆料静置后铜盐溶液和三聚氰胺分层，上层蓝色为铜盐溶液，三聚氰胺沉淀，分层见图11。然后在在鼓风干燥箱中于60℃下烘24h，使去离子水完全挥发，得到混合物；其中，三水合硝酸铜和三聚氰胺的摩尔质量比为1:4。Melamine was added to the copper salt solution, and mechanical stirring was continued for 10 minutes at room temperature until a completely mixed slurry was formed. After standing, the copper salt solution and melamine were separated into layers. The upper blue layer was the copper salt solution, and melamine was precipitated. The layers were shown in Figure 11. Then the mixture was dried at 60°C in a forced air drying oven for 24 hours to completely evaporate the deionized water, and a mixture was obtained; wherein the molar mass ratio of copper nitrate trihydrate to melamine was 1:4.
将混合物研磨成10微米粉体放入坩埚，并用锡纸包裹密闭后，转移到带盖氧化铝坩埚中，然后置于管式炉中，在空气氛围下，以10℃/min的升温速率下升温450℃，反应4h，自然冷却后取出研磨得到含铜氧化物黑褐色粉末。The mixture was ground into 10-micron powder and put into a crucible. After being wrapped and sealed with tin foil, it was transferred to an alumina crucible with a lid. Then, it was placed in a tube furnace and heated to 450°C at a heating rate of 10°C/min in an air atmosphere. The reaction lasted for 4 hours. After natural cooling, the powder was taken out and ground to obtain a dark brown powder containing copper oxide.
对比例2(选取本发明范围以外的载体)Comparative Example 2 (selecting a carrier outside the scope of the present invention)
在烧杯中加入60mL去离子水，称取0.01mol氯化铜加入到烧杯中，室温下机械搅拌至完全溶解即得铜盐溶液。Add 60 mL of deionized water into a beaker, weigh 0.01 mol of copper chloride and add it into the beaker, and stir mechanically at room temperature until it is completely dissolved to obtain a copper salt solution.
向铜盐溶液中加入三聚氰酸，在室温下继续机械搅拌10min，发现无法形成混合均匀的半固态浆料，最终是液体，然后在在鼓风干燥箱中于60℃下烘24h得到少量的蓝色固体，无法进行烧制。其中，氯化铜和三聚氰酸的摩尔质量比为1:4。Cyanuric acid was added to the copper salt solution and mechanical stirring was continued for 10 minutes at room temperature. It was found that a uniformly mixed semi-solid slurry could not be formed, and it was finally a liquid. Then, it was dried in a forced air drying oven at 60°C for 24 hours to obtain a small amount of blue solid, which could not be fired. The molar mass ratio of copper chloride to cyanuric acid was 1:4.
将混合物研磨成10微米粉体放入坩埚，并用锡纸包裹密闭后，转移到带盖氧化铝坩埚中，然后置于管式炉中，在空气氛围下，以10℃/min的升温速率下升温450℃，反应4h，自然冷却后取出研磨得到黑色粉体，是铜的氧化物。The mixture was ground into 10-micron powder and put into a crucible. After being sealed with tin foil, it was transferred to an alumina crucible with a lid. Then, it was placed in a tube furnace and heated to 450°C at a heating rate of 10°C/min in an air atmosphere. The reaction lasted for 4 hours. After natural cooling, the powder was taken out and ground to obtain black powder, which is copper oxide.
对比例3(低于本发明焙烧温度的范围)Comparative Example 3 (lower than the range of calcination temperature of the present invention)
在烧杯中加入60mL去离子水，称取0.01mol氯化铜加入到烧杯中，室温下机械搅拌至完全溶解即得铜盐溶液。Add 60 mL of deionized water into a beaker, weigh 0.01 mol of copper chloride and add it into the beaker, and stir mechanically at room temperature until it is completely dissolved to obtain a copper salt solution.
向铜盐溶液中加入硫脲，在室温下继续机械搅拌10min，至形成完全混合均匀的半固态浆料，然后在在鼓风干燥箱中于60℃下烘24h，使去离子水完全挥发，得到淡蓝色混合物；其中，氯化铜和硫脲的摩尔质量比为1:4。Thiourea was added to the copper salt solution, and mechanical stirring was continued at room temperature for 10 min to form a completely mixed semi-solid slurry, and then dried in a forced air drying oven at 60°C for 24 h to completely evaporate the deionized water to obtain a light blue mixture; wherein the molar mass ratio of copper chloride to thiourea was 1:4.
将淡蓝色混合物研磨成10微米粉体放入坩埚，并用锡纸包裹密闭后，转移到带盖氧化铝坩埚中，然后置于管式炉中，在空气氛围下，以10℃/min的升温速率下升温300℃，反应4h，自然冷却后取出研磨得到晶态铜复合材料。XRD谱图见图12。The light blue mixture was ground into 10 micron powder and placed in a crucible, which was then sealed with tin foil and transferred to an alumina crucible with a lid. The crucible was then placed in a tube furnace and heated to 300°C at a heating rate of 10°C/min in an air atmosphere for 4 hours. The mixture was naturally cooled and then taken out and ground to obtain a crystalline copper composite material. The XRD spectrum is shown in Figure 12.
对比例4(低于本发明焙烧温度的范围)Comparative Example 4 (lower than the range of calcination temperature of the present invention)
在烧杯中加入60mL去离子水，称取0.01mol氯化铜加入到烧杯中，室温下机械搅拌至完全溶解即得铜盐溶液。Add 60 mL of deionized water into a beaker, weigh 0.01 mol of copper chloride and add it into the beaker, and stir mechanically at room temperature until it is completely dissolved to obtain a copper salt solution.
向铜盐溶液中加入硫脲，在室温下继续机械搅拌10min，至形成完全混合均匀的半固态浆料，然后在在鼓风干燥箱中于60℃下烘24h，使去离子水完全挥发，得到淡蓝色混合物；其中，氯化铜和硫脲的摩尔质量比为1:4。Thiourea was added to the copper salt solution, and mechanical stirring was continued at room temperature for 10 min to form a completely mixed semi-solid slurry, and then dried in a forced air drying oven at 60°C for 24 h to completely evaporate the deionized water to obtain a light blue mixture; wherein the molar mass ratio of copper chloride to thiourea was 1:4.
将淡蓝色混合物研磨成10微米粉体放入坩埚，并用锡纸包裹密闭后，转移到带盖氧化铝坩埚中，然后置于管式炉中，在空气氛围下，以10℃/min的升温速率下升温200℃，反应4h，自然冷却后取出研磨得到晶态铜复合材料。XRD谱图见图12。The light blue mixture was ground into 10 micron powder and placed in a crucible, which was then sealed with tin foil and transferred to an alumina crucible with a lid. The crucible was then placed in a tube furnace and heated to 200°C at a heating rate of 10°C/min in an air atmosphere for 4 hours. The crystalline copper composite material was obtained after natural cooling and grinding. The XRD spectrum is shown in Figure 12.
由图12可知，当煅烧温度低于350℃时，复合材料中结构较为复杂，金属铜以晶态铜形式存在。As shown in FIG12 , when the calcination temperature is lower than 350° C., the structure of the composite material is more complex, and the metallic copper exists in the form of crystalline copper.
对比例5(高于本发明焙烧温度的范围)Comparative Example 5 (higher than the range of calcination temperature of the present invention)
在烧杯中加入60mL去离子水，称取0.01mol氯化铜加入到烧杯中，室温下机械搅拌至完全溶解即得铜盐溶液。Add 60 mL of deionized water into a beaker, weigh 0.01 mol of copper chloride and add it into the beaker, and stir mechanically at room temperature until it is completely dissolved to obtain a copper salt solution.
向铜盐溶液中加入硫脲，在室温下继续机械搅拌10min，至形成完全混合均匀的半固态浆料，然后在在鼓风干燥箱中于60℃下烘24h，使去离子水完全挥发，得到淡蓝色混合物；其中，氯化铜和硫脲的摩尔质量比为1:4。Thiourea was added to the copper salt solution, and mechanical stirring was continued at room temperature for 10 min to form a completely mixed semi-solid slurry, and then dried in a forced air drying oven at 60°C for 24 h to completely evaporate the deionized water to obtain a light blue mixture; wherein the molar mass ratio of copper chloride to thiourea was 1:4.
将淡蓝色混合物研磨成10微米粉体放入坩埚，并用锡纸包裹密闭后，转移到带盖氧化铝坩埚中，然后置于管式炉中，在空气氛围下，以10℃/min的升温速率下升温至550℃，反应4h，自然冷却后取出研磨得到墨绿色所述非晶态铜复合材料。The light blue mixture was ground into 10-micron powder and put into a crucible. After being sealed with tin foil, it was transferred to an alumina crucible with a lid. Then, it was placed in a tube furnace and heated to 550°C at a heating rate of 10°C/min in an air atmosphere. The mixture was reacted for 4 hours. After natural cooling, the powder was taken out and ground to obtain the dark green amorphous copper composite material.
对比例6(高于本发明焙烧温度的范围)Comparative Example 6 (higher than the range of calcination temperature of the present invention)
在烧杯中加入60mL去离子水，称取0.01mol氯化铜加入到烧杯中，室温下机械搅拌至完全溶解即得铜盐溶液。Add 60 mL of deionized water into a beaker, weigh 0.01 mol of copper chloride and add it into the beaker, and stir mechanically at room temperature until it is completely dissolved to obtain a copper salt solution.
向铜盐溶液中加入硫脲，在室温下继续机械搅拌10min，至形成完全混合均匀的半固态浆料，然后在在鼓风干燥箱中于60℃下烘24h，使去离子水完全挥发，得到淡蓝色混合物；其中，氯化铜和硫脲的摩尔质量比为1:4。Thiourea was added to the copper salt solution, and mechanical stirring was continued at room temperature for 10 min to form a completely mixed semi-solid slurry, and then dried in a forced air drying oven at 60°C for 24 h to completely evaporate the deionized water to obtain a light blue mixture; wherein the molar mass ratio of copper chloride to thiourea was 1:4.
将淡蓝色混合物研磨成10微米粉体放入坩埚，并用锡纸包裹密闭后，转移到带盖氧化铝坩埚中，然后置于管式炉中，在空气氛围下，以10℃/min的升温速率下升温至600℃，反应4h，自然冷却后取出研磨得到墨绿色所述非晶态铜复合材料。The light blue mixture was ground into 10-micron powder and put into a crucible. After being sealed with tin foil, it was transferred to an alumina crucible with a lid. Then, it was placed in a tube furnace and heated to 600°C at a heating rate of 10°C/min in an air atmosphere. The mixture was reacted for 4 hours. After natural cooling, the powder was taken out and ground to obtain the dark green amorphous copper composite material.
图13为高于本发明焙烧温度范围，即550℃、600℃时的XRD谱图所示，由图可知，温度高时复合材料载体加速缩聚，形成结晶度高的含有非晶态铜的石墨相氮化碳材料，此时已经缩聚完全，很难进行其他方面的应用，且石墨相氮化碳材料产量明显降低。FIG13 is an XRD spectrum at a calcination temperature higher than the present invention, i.e., 550°C and 600°C. As shown in the figure, when the temperature is high, the composite material carrier accelerates the condensation to form a graphite phase carbon nitride material containing amorphous copper with high crystallinity. At this time, the condensation is complete and it is difficult to carry out other applications. In addition, the output of the graphite phase carbon nitride material is significantly reduced.
图14为高于本发明焙烧温度制得复合材料的SEM图(a)和TEM(b)图，由图可知，复合材料表面插层完全消失，通过TEM图可以看出与本发明相比，复合材料表面的孔洞完全消失。FIG14 is an SEM image (a) and TEM image (b) of a composite material obtained at a calcination temperature higher than that of the present invention. It can be seen from the figure that the intercalation layer on the surface of the composite material completely disappears. The TEM image shows that compared with the present invention, the holes on the surface of the composite material completely disappear.
应用例：Application examples:
(1)制备亚铜掺杂氮化碳非均相催化剂(1) Preparation of cuprous carbon nitride-doped heterogeneous catalysts
称取本发明实施例1制备的非晶态铜复合材料置于坩埚中用锡纸密闭，以5℃/min的速率升温至550℃，焙烧4小时，可得到一种非晶态亚铜掺杂氮化碳非均相催化剂，该催化剂对过氧化氢H2O2和过一硫酸盐PMS均有良好的活化效果，可用于类Fenton处理难降解有机废水。由本发明非晶态复合材料制得的该非晶态亚铜掺杂氮化碳非均相催化剂的BET面积达到20.0m2/g，是纯g-C3N4的2.5倍。如图15所示，该非晶态亚铜掺杂氮化碳非均相催化剂可对罗丹明B，缩写为RhB、甲基橙，缩写为MO、亚甲基蓝，缩写为MB和苯酚，缩写为Phenol有良好的降解效果。The amorphous copper composite material prepared in Example 1 of the present invention is weighed and placed in a crucible and sealed with tin foil, and the temperature is raised to 550°C at a rate of 5°C/min, and roasted for 4 hours to obtain an amorphous cuprous carbon nitride heterogeneous catalyst, which has a good activation effect on hydrogen peroxide H2O2 and peroxymonosulfate PMS, and can be used for Fenton-like treatment of refractory organic wastewater. The BET area of the amorphous cuprous carbon nitride heterogeneous catalyst prepared from the amorphous composite material of the present invention reaches 20.0m2 /g, which is 2.5 times that of pure gC3N4 . As shown in Figure 15, the amorphous cuprous carbon nitride heterogeneous catalyst can have a good degradation effect on rhodamine B, abbreviated as RhB, methyl orange, abbreviated as MO, methylene blue, abbreviated as MB and phenol, abbreviated as Phenol.
(2)制备氮化碳负载单原子铜催化剂(2) Preparation of carbon nitride-supported single-atom copper catalyst
称取本发明制备的非晶态铜复合材料与尿素质量比为1:8进行研磨混合均匀，置于坩埚中用锡纸密闭，以5℃/min的速率升温至550℃，焙烧4小时，可制得一种高比表面积的氮化碳负载单原子铜催化剂。由图16可知，该氮化碳负载单原子铜催化剂具有非常蓬松的结构，属于典型的介孔结构材料，BET面积达到89.96m2/g，是纯g-C3N4的11.2倍。由图17可知，该氮化碳负载单原子铜催化剂在较宽pH活化H2O2和PMS降解污染物，这克服了传统Fenton反应pH需要在2～3的不足，可广泛用于类Fenton处理难降解有机废水。The amorphous copper composite material prepared by the present invention and urea are weighed in a mass ratio of 1:8, ground and mixed evenly, placed in a crucible and sealed with tin foil, heated to 550°C at a rate of 5°C/min, and calcined for 4 hours to obtain a carbon nitride-supported single-atom copper catalyst with a high specific surface area. As shown in Figure 16, the carbon nitride-supported single-atom copper catalyst has a very fluffy structure and is a typical mesoporous structure material. The BET area reaches 89.96m2 /g, which is 11.2 times that of pure gC3N4 . As shown in Figure 17, the carbon nitride-supported single-atom copper catalyst activates H2O2 and PMS to degrade pollutants in a wide pH range, which overcomes the deficiency that the traditional Fenton reaction needs to have a pH of 2 to 3, and can be widely used in Fenton-like treatment of difficult-to-degrade organic wastewater.
(3)制备双金属掺杂复合催化剂(3) Preparation of bimetallic doped composite catalysts
含钴前驱体的制备：将4g三聚氰胺和0.02g五水合氯化钴研磨混合均匀得到含钴前驱体。Preparation of a cobalt-containing precursor: 4 g of melamine and 0.02 g of cobalt chloride pentahydrate were ground and mixed to obtain a cobalt-containing precursor.
双金属掺杂复合催化剂的制备：用本发明制备的非晶态铜1.5g与制得的含钴前驱体研磨混合均匀后，置于坩埚中用锡纸密封包裹后以2.5℃/min升温速率升温至550℃，焙烧4h，得到Cu、Co共掺杂氮化碳复合催化剂，记为Cu/Co-CN。Preparation of bimetallic doped composite catalyst: 1.5 g of amorphous copper prepared by the present invention and the prepared cobalt-containing precursor were ground and mixed evenly, placed in a crucible, sealed with tin foil, and heated to 550° C. at a heating rate of 2.5° C./min, and calcined for 4 h to obtain a Cu, Co co-doped carbon nitride composite catalyst, recorded as Cu/Co-CN.
Cu/Co-CN的BET面积达到110.53m2/g，且复合材料中铜仍然以非晶态亚铜形式稳定存在。由图18可知，Cu/Co-CN在较宽的pH范围可活化H2O2降解污染物，可作为非均相催化剂用于难降解废水的类Fenton处理。The BET area of Cu/Co-CN reaches 110.53 m 2 /g, and the copper in the composite material still exists stably in the form of amorphous cuprous. As shown in Figure 18, Cu/Co-CN can activate H 2 O 2 to degrade pollutants in a wide pH range and can be used as a heterogeneous catalyst for Fenton-like treatment of difficult-to-degrade wastewater.
尽管已描述了本发明的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例作出另外的变更和修改。所以，所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。Although the preferred embodiments of the present invention have been described, those skilled in the art may make other changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.
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