CN105905936A - Cuprous oxide nanocrystalline assembly - Google Patents
Cuprous oxide nanocrystalline assembly Download PDFInfo
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- CN105905936A CN105905936A CN201610230151.5A CN201610230151A CN105905936A CN 105905936 A CN105905936 A CN 105905936A CN 201610230151 A CN201610230151 A CN 201610230151A CN 105905936 A CN105905936 A CN 105905936A
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- cuprous oxide
- oxide nanocrystalline
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title abstract description 25
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title abstract description 6
- 229940112669 cuprous oxide Drugs 0.000 title abstract description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 46
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 42
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 23
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 22
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 22
- 229960003638 dopamine Drugs 0.000 claims abstract description 21
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims abstract description 18
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940116269 uric acid Drugs 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 239000002086 nanomaterial Substances 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims abstract description 7
- 230000005415 magnetization Effects 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 230000001788 irregular Effects 0.000 claims abstract description 5
- 101100352912 Caenorhabditis elegans tax-6 gene Proteins 0.000 claims description 49
- 101100352914 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cna-1 gene Proteins 0.000 claims description 49
- 239000000126 substance Substances 0.000 claims description 17
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000002159 nanocrystal Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000001338 self-assembly Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 230000033116 oxidation-reduction process Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000001903 differential pulse voltammetry Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical class [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
Belonging to the technical field of transition metal oxides, the invention relates to a cuprous oxide nanocrystalline assembly. The cuprous oxide nanocrystalline assembly comprises a CAN-1 structure and a CAN-2 structure, the CAN-1 is an irregular micrometer-scale flower cluster like structure, the CAN-2 is a regular spherical structure with narrow particle size distribution. The saturation magnetization intensity of the CAN-1 and the CAN-2 are 3.2emu/g and 9.2emu/g respectively, and the purity is more than 98%. The cuprous oxide nanocrystalline assembly can perform electrocatalysis on ascorbic acid, dopamine and uric acid, adsorb organic molecules and catalyze oxygen reduction reaction. The structure size of the assembly is inversely proportional to electrocatalytic selectivity, adsorption capacity and electrocatalytic ability. The cuprous oxide nanocrystalline assembly is a nano-material used for multifunctional sensors, and has the advantages of excellent structure and performance, simple process, reliable principle, low cost, high product purity, good electromagnetic properties, wide application, and using environmental friendliness.
Description
Technical field:
The invention belongs to transition metal oxide technical field, the Red copper oxide particularly relating to a kind of weak magnetic is received
The brilliant assembly of rice.
Background technology:
Red copper oxide is a kind of important in fields such as agricultural, coating, glass, plastics, pottery and Industrial Catalysis
Inorganic Chemicals, be widely used.Such as, the antibacterial in agricultural and the additive in feedstuff, coating work
The coloring agent etc. in anti-fouling agent, glass industry and ceramic industry in industry.Red copper oxide belongs to p-type semiconductor
Material, the band-gap energy low due to it and the high absorption coefficient of light, and its cheap price and hypotoxicity,
Through being used as gas sensor, high efficiency photocatalyst, eelctro-catalyst and heterogeneous catalyst；Along with synthetic technology
Developing rapidly, the preparation of cuprous nano material has been achieved with rapid progress, many method such as solvent thermal/water
The methods such as thermal synthesis and low temperature liquid phase synthesis have had been reported for multiple cuprous nano material, including multiaspect
The synthesis of body, thin film, nanocages, hollow ball, loose structure etc..Currently, inorganic nano-crystal cluster/assembling
The primary reconstruction preparation of body focuses primarily upon magnetic Nano material, and reaction condition is the harshest, such as synthesis temperature
Spend higher, the response time is longer.The most under cryogenic, preparation realizes weak magnetic based on water solution system
Or the nanocrystalline cluster/assembly of non-magnetic inorganic still faces significant challenge.Therefore, research is prepared Red copper oxide and is received
The brilliant assembly of rice has broad application prospects and huge economic benefit.
Summary of the invention:
It is an object of the invention to overcome the shortcoming of prior art, seek to prepare the Red copper oxide of a kind of weak ferromagnetism
Nanometer crystal assembly, by mol ratio and the reaction temperature of regulation and control pre-reaction material, prepares various sizes of oxidation
Cuprous nanocrystal, by the noncovalent interaction driving ordered fabrication between cuprous nano crystal grain
Become.
To achieve these goals, the cuprous nano crystalline substance assembly that the present invention relates to, including CNA-1 and
Two kinds of physical dimensions of CNA-2, wherein, CNA-1 is irregular micro-meter scale flowers shape structure, a size of
1.8 ± 0.3 μm, are formed by interting to assemble by the cuprous nano crystal grain that crystal size is 32nm；CNA-2
For rule and the spherical structure of narrower particle size distribution, a size of 0.6 ± 0.2 μm, crystal size it is 10nm
Cuprous nano crystal grain by being self-assembly of in order in situ, CNA-2 rough and have little granule
Protruding；The saturation magnetization of CNA-1 and CNA-2 is respectively 3.2emu/g and 9.2emu/g, and purity is big
In 98%, it is possible to Ascorbic Acid (AA), dopamine (DA) and uric acid (UA) electro-catalysis, adsorb organic
Molecule, catalytic oxidation-reduction reacts；The physical dimension of cuprous nano crystalline substance assembly and electro-catalysis selectivity, suction
Attached ability and electro-catalysis ability are inversely proportional to；High-quality nano material for Multifunction Sensor.
The present invention passes through low temperature liquid phase synthetic technology scheme, former with the cuprous presoma of ascorbic acid reduction-oxidation
Reason, prepares the cuprous nano crystalline substance assembly of two kinds of different structure sizes of CNA-1 and CNA-2, and it is concrete
Technical process comprises the following steps:
Copper sulfate and the ammonium bicarbonate aqueous solution that 30ml concentration is 6mmol that 120ml concentration is 3mmol are existed
There-necked flask is heated with stirring to after mix homogeneously 45-50 DEG C keep 20 minutes, adds 45mmol Vitamin C
Aqueous acid reduces, and reduction reaction collects precipitate after 60 minutes, then with deionized water precipitate carried out from
Temperature control 50-60 DEG C drying, the named CNA-1 of collected precipitate after heart washing；Again by above-mentioned steps
Copper sulfate change the Schweinfurt green of concentration 3mmol into, ammonium bicarbonate concentration is 12mmol and aqueous ascorbic acid
Concentration is 45mmol, and in there-necked flask, after mix homogeneously, the agitating heating time is 90 minutes, uses identical
The named CNA-2 of precipitate that preparation flow obtains；CNA-1 and CNA-2 is respectively two kinds of cuprous nanos
Brilliant assembly sample.
Compared with prior art, its product structure and function admirable, preparation technology is simple, preparation principle for the present invention
Reliably, preparation cost is low, and product purity is high, and electromagnetic property is good, is widely used, and uses environmental friendliness.
Accompanying drawing illustrates:
Fig. 1 is the X-ray diffractogram of (a) CNA-1 and (b) CNA-2 prepared by the present invention.
Fig. 2 is (a, c) CNA-1 and (b, d) scanning electron microscope diagram of CNA-2 prepared by the present invention.
Fig. 3 is the nitrogen adsorption/desorption curve of (A) CNA-1 and (B) CNA-2 prepared by the present invention, (C)
The BJH pore size distribution curve of CNA-1 and (D) CNA-2.
Fig. 4 is the magnetic hysteresis curve (A) of (a) CNA-1 and (b) CNA-2 prepared by the present invention, and (B) is
The partial enlarged drawing of figure (A).
Fig. 5 is that (a) CNA-1/GCE and (b) CNA-2/GCE prepared by the present invention is containing AA, DA respectively
With the cyclic voltammetry curve in UA electrolyte.
Fig. 6 is that (a) CNA-1/GCE and (b) CNA-2/GCE prepared by the present invention contains AA (1 at the same time
Mmol/L), the differential pulse voltammetry curve in DA (0.8mmol/L) and UA (1mmol/L) electrolyte.
Fig. 7 is that (A) CNA-1/GCE of preparing of the present invention and (B) CNA-2/GCE is at AA (1mmol/L)
Constant with UA (1mmol/L) concentration, during change DA concentration (mmol/L) differential pulse voltammetry curve: (a)
0.1；(b)0.2；(c)0.3；(d)0.4；(e)0.5；(f)0.6；(g)0.7；(h)0.8.
Fig. 8 is product of the present invention (A) CNA-1 and (B) CNA-2 UV, visible light to Congo red at dark
Absorption spectrum spectrogram: (a) 0min, (b) 10min, (c) 20min, (d) 30min, (e) 40min,
(f) 50min, (g) 60min, (h) 70min, (i) 80min, (g) 90min, (k) 120min,
(l) 140min, (m) 160min, (n) 180min.
CNA-1 (a) and CNA-2 (b) at dark is bent to the rate of adsorption of Congo red for Fig. 9 product of the present invention
Line.
Figure 10 be (a) CNA-1/GCE of preparing of the present invention and (b) CNA-2/GCE (a, b) oxygen saturated or
(A) cyclic voltammetry curve recorded in c 0.1mol/L KOH solution that () nitrogen is saturated and (B) are linear
Scanning volt-ampere curve.
Detailed description of the invention:
Below by embodiment and combine accompanying drawing and be described further.
A kind of cuprous nano crystalline substance assembly, including two kinds of physical dimensions of CNA-1 and CNA-2, wherein,
CNA-1 is irregular micro-meter scale flowers shape structure, and a size of 1.8 ± 0.3 μm, are 32nm by crystal size
Cuprous nano crystal grain by intert assemble formed；CNA-2 is rule and the spherical junctions of narrower particle size distribution
Structure, a size of 0.6 ± 0.2 μm, by the cuprous nano crystal grain that crystal size is 10nm by having in situ
Sequence is self-assembly of, CNA-2 rough and have little granule protruding；The saturated magnetic of CNA-1 and CNA-2
Changing intensity and be respectively 3.2emu/g and 9.2emu/g, purity is more than 98%, it is possible to Ascorbic Acid (AA),
Dopamine (DA) and uric acid (UA) electro-catalysis, adsorb organic molecule, and catalytic oxidation-reduction reacts；Red copper oxide
The physical dimension of nanometer crystal assembly is inversely proportional to electro-catalysis selectivity, absorbability and electro-catalysis ability；For
The high-quality nano material of Multifunction Sensor.
Embodiment 1: prepared by cuprous nano crystalline substance assembly
CuSO by 120mL 3mmol4·5H2O solution and 30mL 6mmol NH4HCO3Solution mix homogeneously
After transfer to 50 DEG C of agitating heating 20min of temperature control in the there-necked flask of 200mL, add 15mL 0.9mmol
Ascorbic acid solution, keep stirring under identical heating-up temperature 1h；Then there-necked flask removal is cooled to room
Temperature, collects brick-red precipitate, and with deionized water centrifuge washing and dry, the precipitate sample of collection is named
CNA-1；The synthetic method of CNA-2 is similar with CNA-1, is a difference in that and changes raw material into 3mmol
Cu(CH3COO)2·5H2The NH of O, 12mmol4HCO3And the ascorbic acid of 4.5mmol, change heat time heating time
For 1.5h.
Fig. 1 is the X-ray energy spectrogram of two kinds of products of CNA-1 and CNA-2, and by Tu Ke get, all of product are spread out
Penetrate the standard diffraction peak all with Red copper oxide (JCPDS, No.05-0667), the peak to match, i.e. 29.60 °,
36.52 °, 42.44 °, cuprous with pure zirconia respectively (110) of the diffraction maximum that occurs of 61.54 ° and 73.69 °,
(111), (200), (220) corresponding with (311) face, show that obtained precipitate sample is oxidation Asia
Copper, and there is no any impurity；Diffraction maximum in analysis chart 1 can obtain, the strongest diffraction maximum ((111) of CNA-2
Face) wider, and the diffraction maximum in CNA-1 (111) face point and narrow, crystallization chi nanocrystalline in CNA-1 is described
Very little bigger；According to thanking to Le formula, half-peak breadth based on (111) crystallographic plane diffraction peak can be calculated in CNA-1
Nanocrystalline crystalline size is 32nm, and crystalline size nanocrystalline in CNA-2 is 10nm；
Fig. 2 is the scanning electron microscope diagram of Red copper oxide, Fig. 2 a, CNA-1 sample be irregular
Micro-meter scale flowers shape structure, size is about 1.8 ± 0.3 μm；Fig. 2 c by amplification is visible, flowers
The Red copper oxide sample of shape micron-scale by the cuprous nano crystalline substance of reduced size by intert assemble and
Formed；CNA-2 sample is then more regular and the spherical structure (Fig. 2 b) of narrower particle size distribution, statistics
Analyze and find that the particle size of CNA-2 is less, be 0.6 ± 0.2 μm；Can clearly see from Fig. 2 d amplified
The surface observing CNA-2 sample is not the most the most smooth and has a lot of little granule protruding, shows CNA-2
It is to be formed by self assembly the most in order by the cuprous nano crystalline substance of reduced size；By prepared sample
Scanning electron microscope diagram is it can be seen that gained Red copper oxide product is nanometer crystal assembly structure；
Fig. 3 is nitrogen adsorption/desorption curve and the BJH pore size distribution curve of CNA-1 and CNA-2；Such as figure
Shown in 3, the absorption/desorption curve of CNA-1 and CNA-2 is IV type, and has time stagnant circle of H1 type；
The average pore size of CNA-1 and CNA-2 is respectively 23.4nm and 13.2nm, shows to be synthesized by this system
Red copper oxide is meso-hole structure, and this result is that the structure of cuprous nano crystalline substance assembly determines and provides support；
Experiment records the specific surface area of CNA-1 and CNA-2 and pore volume is respectively 3.0m2/ g and 0.018cm3/g
And 20.0m2/ g and 0.066cm3/ g, this with sem observation to conclusion match.
Embodiment 2: the magnetic performance of cuprous nano crystalline substance assembly measures
Fig. 4 is the room temperature hysteresis curve of CNA-1 and CNA-2, by vibrating specimen magnetometer in magnetic field intensity is
1.4×104Gained is measured under Oe；Fig. 4 A is that CNA-1 and CNA-2 sample is in the range of whole magnetic field intensity
Magnetic property curve；CNA-1 sample shows the hysteresis curve typically with saturation magnetization, and
Although the hysteresis curve of CNA-2 sample less meets with conventional shape, however still show compared with fractional value saturated
The intensity of magnetization；From hysteresis curve partial enlarged view (Fig. 4 B), the magnetization of CNA-1 and CNA-2 is bent
Line all demonstrates a relatively small B-H loop, and this shows that CNA-1 and CNA-2 sample is weak ferromagnetism.
Embodiment 3: the preparation of modified electrode
It is the suspension of 1.5mg/mL with secondary water and cuprous nano crystalline substance assembly configuration concentration, uniformly divides
Take 10 μ L after Saning to be added drop-wise on glass-carbon electrode, under room temperature be dried, be respectively designated as CNA-1/GCE and
CNA-2/GCE。
Embodiment 4: the electrocatalysis characteristic of Red copper oxide modified electrode measures
Fig. 5 utilizes two kinds of Red copper oxide assembly modified electrode Ascorbic Acids of cyclic voltammetric technique study
(AA), dopamine (DA) and the electro catalytic activity of uric acid (UA)；The oxidation peak of DA and UA is obvious,
And the oxidation peak of AA is wider and catalytic current is relatively low；Comparison diagram 5a and b, AA containing same concentrations,
In the solution of DA or UA, the peak point current of CNA-2/GCE is significantly greater than CNA-1/GCE, shows CNA-2/GCE
There is more preferable electro catalytic activity；
Fig. 6 represents in the case of ascorbic acid, dopamine and three kinds of biomolecule of uric acid coexist, CNA-2/GCE
DA and UA can be detected simultaneously, and CNA-1/GCE has been merely able to the detection to DA, this and the survey of Fig. 5
Test result is consistent；
Fig. 7 is CNA-1/GCE (A) and CNA-2/GCE (B) is at AA (1mmol/L) and UA (1mmol/L)
Concentration is constant, changes DPV curve obtained during DA concentration；Illustration from Fig. 7, Red copper oxide
The catalysis peak point current of assembly modified electrode is along with the most linear increase of the increase of DA concentration, CNA-1/GCE
It is respectively r=0.9935 and r=0.9827 with the linearly dependent coefficient of CNA-2/GCE；The existence of AA and UA is not
The detection of DA can be affected, although the detection of AA, UA can be affected by DA；Comparison diagram 7A and B is visible, CNA-2/GCE
In three kinds of mixed liquors, the detection to DA has more preferable selectivity and higher sensitivity than CNA-1/GCE.
Embodiment 5: the absorption property of Red copper oxide modified electrode measures
Transition metal oxide can remove debirs by absorption or catalytic property subsequently from aqueous solution.This
Embodiment with Congo red as adsorbate, the absorption property of prepared cuprous nano crystalline substance assembly；Experiment knot
Fruit shows, cuprous nano crystalline substance assembly is in dark condition, natural optical condition and xenon lamp (300W) condition
Under identical to the absorption result of Congo red, show that Congo red is mainly adsorbed onto Red copper oxide by adsorption and receives
On the brilliant assembly of rice；Fig. 8 shows that CNA-1 and CNA-2 all has obvious adsorption to Congo red；Fig. 9
It is shown that adsorption efficiency that the Adsorption experimental results according to Fig. 8 the described change curve with adsorption time；
CNA-2 has more preferable absorbability than CNA-1, and when adsorption time is 2h, CNA-1 adsorbance base
Originally maximum (1.22mg/10mg, Congo red/Red copper oxide) is reached；And CNA-2 is in the 3h of experiment
Saturated still without reaching to adsorb, and its absorbability is more weak；By CNA-2 has less cuprous nano
The loose structure that brilliant and specific group assembling structure is formed is caused.
Embodiment 6: the hydrogen reduction performance measurement of Red copper oxide modified electrode
The reaction mechanism of cuprous oxide catalysis oxygen reduction is: in controlled potential range, along with single order oxygen
The existence of dividing potential drop, it should have a speed limit electron transfer adsorption of oxygen to form the superoxides (public affairs of Red copper oxide
Formula 8-1) process, relate to the concurrent reaction (formula 8-2) of a water simultaneously；(figure in the saturated electrolyte of nitrogen
10A), the cyclic voltammetry curve of modified electrode does not has characteristic peak substantially, and in the saturated electrolyte of oxygen
-0.46V has significant negative electrode peak to occur, Figure 10 B linear sweep voltammetry curve also leads to the same conclusion,
Show that cuprous nano crystalline substance assembly has potential catalysis activity to oxygen reduction；
Cu2O-O2+e-→Cu2O-O2 - (1)
Cu2O-O2+H2O+e-→Cu2O-HO2+OH- (2)。
Claims (2)
1. a cuprous nano crystalline substance assembly, it is characterized in that: include two kinds of physical dimensions, it is respectively designated as CNA-1 and CNA-2, wherein, CNA-1 is irregular micro-meter scale flowers shape structure, a size of 1.8 ± 0.3 μm, are formed by interting to assemble by the cuprous nano crystal grain that crystal size is 32nm；CNA-2 is rule and the spherical structure of narrower particle size distribution, a size of 0.6 ± 0.2 μm, by the cuprous nano crystal grain that crystal size is 10nm by being self-assembly of in order in situ, and CNA-2 rough and have little granule protruding；The saturation magnetization of CNA-1 and CNA-2 is respectively 3.2emu/g and 9.2emu/g, and purity is more than 98%, it is possible to Ascorbic Acid, dopamine and uric acid electro-catalysis, adsorbs organic molecule, and catalytic oxidation-reduction reacts；Its physical dimension is inversely proportional to electro-catalysis selectivity, absorbability and electro-catalysis ability；Nano material for Multifunction Sensor.
Cuprous nano crystalline substance assembly the most according to claim 1, it is characterised in that its concrete preparation process includes:
Copper sulfate and the ammonium bicarbonate aqueous solution that 30ml concentration is 6mmol that 120ml concentration is 3mmol are heated with stirring to 45-50 DEG C of holding 20 minutes in there-necked flask after mix homogeneously, add the reduction of 45mmol aqueous ascorbic acid, reduction reaction collects precipitate after 60 minutes, temperature control 50-60 DEG C drying, the named CNA-1 of collected precipitate after precipitate being centrifuged washing with deionized water again；Change the copper sulfate in above-mentioned steps the Schweinfurt green of concentration 3mmol into again, ammonium bicarbonate concentration is 12mmol and aqueous ascorbic acid concentration is 45mmol, in there-necked flask, after mix homogeneously, the agitating heating time is 90 minutes, the named CNA-2 of precipitate using identical preparation flow to obtain.
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| CN106966422A (en) * | 2017-04-01 | 2017-07-21 | 华南理工大学 | A kind of pair of cuprous microballoon of spherical alumina and preparation method thereof |
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