CN105905936B - A kind of cuprous nano crystalline substance assembly - Google Patents
A kind of cuprous nano crystalline substance assembly Download PDFInfo
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- CN105905936B CN105905936B CN201610230151.5A CN201610230151A CN105905936B CN 105905936 B CN105905936 B CN 105905936B CN 201610230151 A CN201610230151 A CN 201610230151A CN 105905936 B CN105905936 B CN 105905936B
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- 239000000126 substance Substances 0.000 title claims abstract description 18
- 101100352912 Caenorhabditis elegans tax-6 gene Proteins 0.000 claims abstract description 53
- 101100352914 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cna-1 gene Proteins 0.000 claims abstract description 53
- 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 42
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 23
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 21
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 21
- 229960003638 dopamine Drugs 0.000 claims abstract description 20
- 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
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 230000005415 magnetization Effects 0.000 claims abstract description 7
- 230000001788 irregular Effects 0.000 claims abstract description 4
- 238000006479 redox reaction Methods 0.000 claims abstract description 4
- 239000002159 nanocrystal Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000001338 self-assembly Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 3
- 101100271206 Arabidopsis thaliana ATHB-15 gene Proteins 0.000 abstract 1
- 101100352903 Homo sapiens PPP3CA gene Proteins 0.000 abstract 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 18
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 18
- 229940112669 cuprous oxide Drugs 0.000 description 18
- 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
- 239000010949 copper Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 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
- 229910001868 water Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001903 differential pulse voltammetry Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- 150000000996 L-ascorbic acids Chemical class 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000002474 experimental 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
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 238000004847 absorption spectroscopy 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
- 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
- 239000003899 bactericide agent Substances 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000001276 controlling effect Effects 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 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
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003317 industrial substance 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
- 230000003287 optical effect Effects 0.000 description 1
- -1 oxygen form superoxides Chemical class 0.000 description 1
- 239000012071 phase Substances 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
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- 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
- 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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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic 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
- 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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- B01J35/33—
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- B01J35/40—
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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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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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- C01P2002/00—Crystal-structural characteristics
- 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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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The invention belongs to transition metal oxide technical field, is related to a kind of cuprous nano crystalline substance assembly, including 2 two kinds of structures of CNA 1 and CNA, and CNA 1 is irregular micro-meter scale flowers shape structure, and CNA 2 is the spherical structure of rule and narrower particle size distribution；CNA 1 and CNA 2 saturation magnetization are respectively 3.2emu/g and 9.2emu/g, and purity is more than 98%；Can Ascorbic Acid, dopamine and uric acid electro-catalysis, adsorb organic molecule and catalytic oxidation-reduction reaction；Its physical dimension is inversely proportional with electro-catalysis selectivity, adsorption capacity and electro-catalysis ability；Nano material for Multifunction Sensor；Its structure and function admirable, technique is simple, and principle is reliable, and cost is low, and product purity is high, and electromagnetic property is good, is widely used, and use environment is friendly.
Description
Technical field：
It is brilliant more particularly to a kind of cuprous nano of weak magnetic the invention belongs to transition metal oxide technical field
Assembly.
Background technology：
Cuprous oxide is a kind of important inorganic in fields such as agricultural, coating, glass, plastics, ceramics and Industrial Catalysis
Industrial chemicals, it is widely used.For example, the additive in bactericide and feed in agricultural, the anti-fouling agent in coatings industry, glass
Colouring agent in industry and ceramic industry etc..Cuprous oxide belongs to p-type semiconductor material, due to its low band-gap energy and height
The absorption coefficient of light, and its cheap price and hypotoxicity are utilized as gas sensor, high efficiency photocatalyst, electricity and urged
Agent and heterogeneous catalyst；With the rapid development of synthetic technology, the preparation of cuprous nano material have been achieved with it is considerable enter
The methods of step, many methods such as solvent heat/Hydrothermal Synthesiss and low temperature liquid phase synthesize has had been reported for a variety of cuprous nanos
Material, include the synthesis of polyhedron, film, nanocages, hollow ball, loose structure etc..Currently, inorganic nano-crystal cluster/assembling
The primary reconstruction of body prepares and focuses primarily upon magnetic Nano material, and reaction condition is more harsh, as synthesis temperature is higher, anti-
It is longer etc. between seasonable.How under cryogenic, prepare and realize that weak magnetic or non-magnetic inorganic are nanocrystalline based on water solution system
Cluster/assembly still faces significant challenge.Therefore, research prepares cuprous nano crystalline substance assembly and had broad application prospects
With huge economic benefit.
The content of the invention：
The shortcomings that it is an object of the invention to overcome prior art, seek to prepare a kind of cuprous nano of weak ferromagnetism
Brilliant assembly, by regulating and controlling the mol ratio and reaction temperature of pre-reaction material, various sizes of cuprous nano crystal grain is prepared,
Ordered fabrication is driven to form by the noncovalent interaction between cuprous nano crystal grain.
To achieve these goals, cuprous nano crystalline substance assembly of the present invention, including CNA-1 and CNA-2 two
Kind physical dimension, wherein, CNA-1 is irregular micro-meter scale flowers shape structure, and size is 1.8 ± 0.3 μm, by crystal size
Formed for 32nm cuprous nano crystal grain by interspersed assembling；CNA-2 is the spherical structure of rule and narrower particle size distribution,
Size is 0.6 ± 0.2 μm, is self-assembly of in order by original position by the cuprous nano crystal grain that crystal size is 10nm,
CNA-2 rough and there is little particle raised；CNA-1 and CNA-2 saturation magnetization be respectively 3.2emu/g and
9.2emu/g, purity be more than 98%, can Ascorbic Acid (AA), dopamine (DA) and uric acid (UA) electro-catalysis, adsorb it is organic
Molecule, catalytic oxidation-reduction reaction；The physical dimension of cuprous nano crystalline substance assembly and electro-catalysis selectivity, adsorption capacity and electricity
Catalytic capability is inversely proportional；High quality nanomaterials for Multifunction Sensor.
The present invention is by low temperature liquid phase synthetic technology scheme, with the principle of the cuprous presoma of ascorbic acid reduction-oxidation, system
The cuprous nano crystalline substance assembly of two kinds of different structure sizes of standby CNA-1 and CNA-2, its specific embodiment include following step
Suddenly：
By the copper sulphate that 120ml concentration is 3mmol and the ammonium bicarbonate aqueous solution that 30ml concentration is 6mmol in three-necked flask
In be well mixed after be heated with stirring to 45-50 DEG C and kept for 20 minutes, add the reduction of 45mmol aqueous ascorbic acids, reduction is anti-
Sediment is collected after answering 60 minutes, then 50-60 DEG C of temperature control after centrifuge washing is carried out with deionized water to sediment and is dried, is received
The sediment of collection is named as CNA-1；Copper acetate, the ammonium hydrogen carbonate that copper sulphate in above-mentioned steps is changed to concentration 3mmol again are dense
It is 45mmol to spend for 12mmol and aqueous ascorbic acid concentration, and the agitating and heating time is 90 after being well mixed in three-necked flask
Minute, the sediment obtained using identical preparation flow is named as CNA-2；CNA-1 and CNA-2 is respectively two kinds of cuprous oxide
Nanometer crystal assembly sample.
Compared with prior art, its product structure and function admirable, preparation technology is simple, and preparation principle is reliable by the present invention,
It is low to prepare cost, product purity is high, and electromagnetic property is good, is widely used, and use environment is friendly.
Brief description of the drawings：
Fig. 1 is (a) CNA-1 prepared by the present invention and (b) CNA-2 X-ray diffractogram.
Fig. 2 is (a, c) CNA-1 prepared by the present invention and (b, d) CNA-2 scanning electron microscope diagram.
(A) CNA-1 and (B) CNA-2 nitrogen adsorption/desorption curve that Fig. 3 is prepared for the present invention, (C) CNA-1 and (D)
CNA-2 BJH pore size distribution curves.
Fig. 4 is (a) CNA-1 prepared by the present invention and (b) CNA-2 magnetic hysteresis curve (A), and (B) is that the part of figure (A) is put
Big figure.
Fig. 5 is (a) CNA-1/GCE prepared by the present invention and (b) CNA-2/GCE in AA, DA and UA electrolyte is contained respectively
Cyclic voltammetry curve.
Fig. 6 is that (a) CNA-1/GCE prepared by the present invention and (b) CNA-2/GCE contain AA (1mmol/L), DA at the same time
Differential pulse voltammetry curve in (0.8mmol/L) and UA (1mmol/L) electrolyte.
Fig. 7 is (A) CNA-1/GCE prepared by the present invention and (B) CNA-2/GCE in AA (1mmol/L) and UA (1mmol/L)
Concentration is constant, changes differential pulse voltammetry curve during DA concentration (mmol/L)：(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 that product of the present invention (A) CNA-1 and (B) CNA-2 at dark composes to Congo red ultraviolet-visible absorption spectroscopy
Figure：(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.
Fig. 9 products of the present invention at dark CNA-1 (a) and CNA-2 (b) to Congo red adsorpting rate curve.
Figure 10 is (a) CNA-1/GCE prepared by the present invention and (b) CNA-2/GCE in (a, b) oxygen saturation or (c) nitrogen
(A) cyclic voltammetry curve and (B) linear sweep voltammetry curve measured in the 0.1mol/L KOH solutions of saturation.
Embodiment：
It is described further by way of example and in conjunction with the accompanying drawings.
A kind of cuprous nano crystalline substance assembly, including two kinds of physical dimensions of CNA-1 and CNA-2, wherein, CNA-1 is not
The micro-meter scale flowers shape structure of rule, size are 1.8 ± 0.3 μm, by the cuprous nano crystal grain that crystal size is 32nm
Formed by interspersed assembling；CNA-2 is the spherical structure of rule and narrower particle size distribution, and size is 0.6 ± 0.2 μm, by crystallizing
The cuprous nano crystal grain that size is 10nm is self-assembly of in order by original position, CNA-2 rough and has small
Grain is raised；CNA-1 and CNA-2 saturation magnetization is respectively 3.2emu/g and 9.2emu/g, and purity is more than 98%, can be right
Ascorbic acid (AA), dopamine (DA) and uric acid (UA) electro-catalysis, adsorb organic molecule, catalytic oxidation-reduction reaction；Cuprous oxide
The physical dimension of nanometer crystal assembly is inversely proportional with electro-catalysis selectivity, adsorption capacity and electro-catalysis ability；For multi-functional biography
The high quality nanomaterials of sensor.
Embodiment 1：It is prepared by cuprous nano crystalline substance assembly
By 120mL 3mmol CuSO4·5H2O solution and 30mL 6mmol NH4HCO3It is transferred to after solution is well mixed
50 DEG C of agitating and heating 20min of temperature control in 200mL three-necked flask, 15mL 0.9mmol ascorbic acid solution is added, kept
1h is stirred under identical heating-up temperature；Then three-necked flask removes and is cooled to room temperature, collects brick-red sediment, uses deionized water
Centrifuge washing is simultaneously dried, and the sediment sample of collection is named as CNA-1；CNA-2 synthetic method is similar with CNA-1, difference
Place is the Cu (CH that raw material is changed to 3mmol3COO)2·5H2O, 12mmol NH4HCO3And 4.5mmol ascorbic acid, add
The hot time is changed to 1.5h.
Fig. 1 is the X-ray energy spectrogram of two kinds of products of CNA-1 and CNA-2, by Tu Ke get, all diffraction maximums of product all with
The standard diffraction peak of cuprous oxide (JCPDS, No.05-0667) matches, i.e., at 29.60 °, 36.52 °, 42.44 °, 61.54 °
It is corresponding with (110), (111), (200), (220) and (311) face that pure zirconia is cuprous respectively with the diffraction maximum of 73.69 ° of appearance,
Show that obtained sediment sample is cuprous oxide, and there is no any impurity；Diffraction maximum in analysis chart 1 can obtain, CNA-2's
Most strong diffraction maximum ((111) face) is wider, and the diffraction maximum in CNA-1 (111) face is sharp and narrow, illustrates crystallization nanocrystalline in CNA-1
Size is bigger；According to thanking to Le formula, the half-peak breadth based on (111) crystallographic plane diffraction peak can be calculated crystalline substance nanocrystalline in CNA-1
Body size is 32nm, and crystalline size nanocrystalline in CNA-2 is 10nm；
Fig. 2 is the scanning electron microscope diagram of cuprous oxide, and from Fig. 2 a, CNA-1 samples are irregular micron meter
Flowers shape structure is spent, size is about 1.8 ± 0.3 μm；It is visible by Fig. 2 c of amplification, the cuprous oxide sample of flowers shape micron-scale
Product are formed by the cuprous nano crystalline substance of reduced size by interspersed assembling；And CNA-2 samples are then more rule and granularity
The spherical structure (Fig. 2 b) of narrow distribution, statistical analysis find that CNA-2 particle size is smaller, are 0.6 ± 0.2 μm；From amplification
Fig. 2 d can be clearly observable the surfaces of CNA-2 samples and equally not be very smooth and have many little particles raised, show that CNA-2 is
Formed by the cuprous nano crystalline substance of reduced size by self assembly in order in situ；Pass through the scanning electron microscopy of prepared sample
It is nanometer crystal assembly structure that mirror figure, which can be seen that gained cuprous oxide product,；
Fig. 3 is CNA-1 and CNA-2 nitrogen adsorption/desorption curve and BJH pore size distribution curves；As shown in figure 3,
CNA-1 and CNA-2 absorption/desorption curve is IV types, and possesses time stagnant circle of H1 types；CNA-1 and CNA-2 average hole
Footpath is respectively 23.4nm and 13.2nm, and the cuprous oxide for showing to synthesize by the system is meso-hole structure, and the result is sub- for oxidation
The structure determination of copper nanocrystallite assembly provides support；Experiment measures CNA-1 and CNA-2 specific surface area and pore volume difference
For 3.0m2/ g and 0.018cm3/ g and 20.0m2/ g and 0.066cm3/ g, this conclusion phase observed with SEM
It coincide.
Embodiment 2：The magnetic performance measure of cuprous nano crystalline substance assembly
Fig. 4 be CNA-1 and CNA-2 room temperature hysteresis curve, by vibrating specimen magnetometer magnetic field intensity be 1.4 ×
104Gained is measured under Oe；Fig. 4 A are magnetic property curve of the CNA-1 and CNA-2 samples in the range of whole magnetic field intensity；CNA-1
Sample shows the typical hysteresis curve with saturation magnetization, though and the hysteresis curve of CNA-2 samples and conventional shape
So less meet, but still show the saturation magnetization compared with fractional value；Can by hysteresis curve partial enlarged view (Fig. 4 B)
See, CNA-1 and CNA-2 magnetization curve show a relatively small B-H loop, and this shows CNA-1 and CNA-2 samples
For weak ferromagnetism.
Embodiment 3：The preparation of modified electrode
The suspension for being 1.5mg/mL with secondary water and cuprous nano crystalline substance assembly configuration concentration, takes after dispersed
10 μ L are added drop-wise on glass-carbon electrode, are dried at room temperature, are respectively designated as CNA-1/GCE and CNA-2/GCE.
Embodiment 4：The electrocatalysis characteristic measure of cuprous oxide modified electrode
Fig. 5 utilizes two kinds of cuprous oxide assembly modified electrode Ascorbic Acids (AA) of cyclic voltammetric technique study, more
The electro catalytic activity of bar amine (DA) and uric acid (UA)；DA and UA oxidation peak is obvious, and AA oxidation peak is wider and is catalyzed
Electric current is relatively low；Comparison diagram 5a and b, in the solution of AA, DA or UA containing same concentrations, CNA-2/GCE peak point current is bright
It is aobvious to be more than CNA-1/GCE, show that CNA-2/GCE has more preferable electro catalytic activity；
Fig. 6 represents that in the case where three kinds of ascorbic acid, dopamine and uric acid biomolecule coexist CNA-2/GCE can
DA and UA are detected simultaneously, and CNA-1/GCE is merely able to complete the detection to DA, this is consistent with Fig. 5 test result；
Fig. 7 is that CNA-1/GCE (A) and CNA-2/GCE (B) is constant in AA (1mmol/L) and UA (1mmol/L) concentration, is changed
Become DPV curves resulting during DA concentration；From the illustration in Fig. 7, the catalysis peak electricity of cuprous oxide assembly modified electrode
For flow valuve with the substantially linear increase of the increase of DA concentration, CNA-1/GCE and CNA-2/GCE linearly dependent coefficient are respectively r
=0.9935 and r=0.9827；AA and UA presence does not interfere with DA detection, although AA, UA detection can be influenceed by DA；Than
It is visible compared with Fig. 7 A and B, detections of the CNA-2/GCE in three kinds of mixed liquors to DA than CNA-1/GCE possess preferably selectivity and
Higher sensitivity.
Embodiment 5：The absorption property measure of cuprous oxide modified electrode
Transition metal oxide can remove debirs by absorption or subsequent catalytic property from the aqueous solution.This implementation
Example with Congo red for adsorbate, the absorption property of prepared cuprous nano crystalline substance assembly；Test result indicates that oxidation is sub-
Copper nanocrystallite assembly is identical to Congo red absorption result under the conditions of dark condition, natural optical condition and xenon lamp (300W),
Show that Congo red is mainly to be adsorbed onto by suction-operated on cuprous nano crystalline substance assembly；Fig. 8 shows CNA-1 and CNA-2
There is obvious suction-operated to Congo red；Fig. 9 be shown adsorption efficiency that the Adsorption experimental results according to Fig. 8 are described with
The change curve of adsorption time；CNA-2 possesses more preferable adsorption capacity than CNA-1, and when adsorption time is 2h, CNA-1 inhales
Attached amount basically reaches maximum (1.22mg/10mg, Congo red/cuprous oxide)；And CNA-2 in the 3h of experiment still without reaching
Adsorption saturation, and its adsorption capacity is weaker；By having smaller cuprous nano brilliant in CNA-2 and its special package assembly institute
Caused by the loose structure of formation.
Embodiment 6：The hydrogen reduction performance measurement of cuprous oxide modified electrode
The reaction mechanism of cuprous oxide catalysis oxygen reduction is：In controllable potential range, along with single order partial pressure of oxygen
Presence, it should have the transfer of speed limit electronics and adsorption of oxygen form superoxides (formula 8-1) process of cuprous oxide, together
When be related to the concurrent reaction (formula 8-2) of a water；(Figure 10 A), the cyclic voltammetric of modified electrode in nitrogen saturation electrolyte
Curve does not have characteristic peak substantially, and has significant negative electrode peak to occur in -0.46V in oxygen saturation electrolyte, and Figure 10 B are linearly swept
Retouch volt-ampere curve also to lead to the same conclusion, show that there is cuprous nano crystalline substance assembly potential catalysis to live to oxygen reduction
Property；
Cu2O-O2+e-→Cu2O-O2 - (1)
Cu2O-O2+H2O+e-→Cu2O-HO2+OH- (2)。
Claims (1)
- A kind of 1. cuprous nano crystalline substance assembly, it is characterised in that：Including two kinds of physical dimensions, be respectively designated as CNA-1 and CNA-2, wherein, CNA-1 is irregular micro-meter scale flowers shape structure, and size is 1.8 ± 0.3 μm, is by crystal size 32nm cuprous nano crystal grain is formed by interspersed assembling；CNA-2 be rule and narrower particle size distribution spherical structure, chi Very little is 0.6 ± 0.2 μm, is self-assembly of in order by original position by the cuprous nano crystal grain that crystal size is 10nm, CNA-2 It is rough and have little particle raised；CNA-1 and CNA-2 saturation magnetization is respectively 3.2emu/g and 9.2emu/ G, purity be more than 98%, can Ascorbic Acid, dopamine and uric acid electro-catalysis, adsorb organic molecule, catalytic oxidation-reduction reaction； Its physical dimension is inversely proportional with electro-catalysis selectivity, adsorption capacity and electro-catalysis ability；Nanometer material for Multifunction Sensor Material；Its specific preparation process includes：By 120mL 3mmol CuSO4·5H2O solution and 30mL 6mmol NH4HCO3Solution mixes 50 DEG C of agitating and heating 20min of temperature control in 200mL three-necked flask are transferred to after closing uniformly, add the anti-bad of 15mL 0.9mmol Hematic acid solution, keep stirring 1h under identical heating-up temperature；Then three-necked flask removes and is cooled to room temperature, collects brick-red precipitation Thing, with deionized water centrifuge washing and dry, the sediment sample of collection is named as CNA-1；CNA-2 synthetic method and CNA- 1 is similar, is a difference in that the Cu (CH that the raw material in above-mentioned steps is changed to 3mmol3COO)2·5H2O, 12mmol NH4HCO3 And 4.5mmol ascorbic acid, heat time are changed to 1.5h.
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