CN105923647B - A kind of preparation method of the brilliant assembly of cuprous nano - Google Patents

A kind of preparation method of the brilliant assembly of cuprous nano Download PDF

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CN105923647B
CN105923647B CN201610230153.4A CN201610230153A CN105923647B CN 105923647 B CN105923647 B CN 105923647B CN 201610230153 A CN201610230153 A CN 201610230153A CN 105923647 B CN105923647 B CN 105923647B
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CN105923647A (en
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郭培志
王荣跃
桑玉涛
赵修松
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Qingdao University
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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    • C01P2006/17—Pore diameter distribution

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Abstract

The invention belongs to metal oxide preparing technical field, it is related to a kind of preparation method of the brilliant assembly of cuprous nano, pass through low temperature liquid phase synthetic technology scheme, with the principle of the cuprous presoma of ascorbic acid reduction-oxidation, prepare the brilliant assembly of two kinds of various sizes of cuprous nanos, it can be used in detection ascorbic acid, dopamine and uric acid, the assembly modified electrode that the crystalline substance self assembly of small size cuprous nano is obtained, the detected representation to dopamine goes out finer selection and more high sensitivity；Two kinds of nanometer crystal assemblies have suction-operated to Congo red, and the brilliant assembly of less cuprous nano has more preferable adsorption capacity；Its preparation technology is simple, and principle is reliable, and preparation cost is low, and product purity is high, and electromagnetic property is good, is widely used, and use environment is friendly.

Description

A kind of preparation method of the brilliant assembly of cuprous nano
Technical field：
The invention belongs to transition metal oxide preparing technical field, it is related to one kind and a step is used under the conditions of design temperature The method that method synthesis technique prepares the brilliant assembly of weak magnetic cuprous nano.
Background technology：
Cuprous oxide is a kind of important inorganic in fields such as agricultural, coating, glass, plastics, ceramics and Industrial Catalysis Industrial chemicals, 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 developing rapidly for synthetic technology, the preparation of cuprous nano material have been achieved with it is considerable enter Step, the method such as many methods such as solvent heat/Hydrothermal Synthesiss and low temperature liquid phase synthesis has had been reported for a variety of cuprous nanos Material, includes 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, and such as synthesis temperature is higher, anti- It is longer etc. between seasonable.How under cryogenic, based on water solution system realize weak magnetic or the nanocrystalline cluster of non-magnetic inorganic/ The preparation of assembly still faces significant challenge.Therefore, the preparing technique process of the brilliant assembly of research cuprous nano has wide Wealthy application prospect and huge economic benefit.
The content of the invention：
It is an object of the invention to overcome the shortcoming that existing synthetic technology is present, propose that one kind synthesizes skill using low temperature liquid phase Art technique, is built by synthesis system, prepares a kind of brilliant assembly of the cuprous nano of sub-micron or micron-scale.
To achieve these goals, the present invention is sub- with ascorbic acid reduction-oxidation by low temperature liquid phase synthetic technology scheme The principle of copper presoma, prepares the brilliant assembly of two kinds of various sizes of cuprous nanos；Its specific embodiment includes following Step：
The ammonium bicarbonate aqueous solution that the copper sulphate for being 3mmol by 120ml concentration and 30ml concentration are 6mmol is 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；Carry out after centrifuge washing 50-60 DEG C of temperature control to sediment with deionized water again and dry, collect Sediment is named as CNA-1；The copper sulphate in above-mentioned steps is changed to the copper acetate that concentration is 3mmol again, concentration is 12mmol Ammonium hydrogen carbonate and concentration be 45mmol aqueous ascorbic acid, in three-necked flask be well mixed after the agitating and heating time be 90 minutes, the sediment obtained using identical preparation flow was named as CNA-2；CNA-1 and CNA-2 are respectively that two kinds of oxidations are sub- Copper nanocrystallite assembly sample, its sample purity is more than 98%；By regulating and controlling the mol ratio and reaction temperature of pre-reaction material, system The standby brilliant assembly of various sizes of cuprous nano, its crystal size is 10nm crystal grain by being self-assembly of 0.6 μ in order The brilliant assembly of m cuprous nano, the brilliant assembly of cuprous nano of 1.8 μ m in size is by oxidation of the crystal size for 32nm Cuprous crystal grain is constituted；The brilliant assembly of two kinds of cuprous nanos all has the saturated magnetization of weak ferromagnetism, its CNA-1 and CNA-2 Intensity is respectively 3.2emu/g and 9.2emu/g；Cuprous nano crystalline substance assembly has electrocatalysis characteristic to DA, UA and AA's, There is absorption property to organic molecule, there is catalytic performance, the brilliant group of cuprous nano of relative small size to oxygen reduction reaction Electro-catalysis selectivity, adsorption capacity and the electro-catalysis ability for filling body are more excellent；Cuprous nano crystalline substance assembly is used for many work( The nano material of energy sensor.
Cuprous oxide colloid nanocrystalline assembly prepared by the present invention be formed by cuprous nano it is brilliant between The ordered fabrication that noncovalent interaction (including Van der Waals force, magnetic interaction etc.) is driven is formed；Two kinds various sizes of The surface of cuprous oxide colloid nanocrystalline assembly is smooth；CNA-1 samples are irregular micro-meter scale flowers shape structure, size For 1.8 ± 0.3 μm, formed by the cuprous nano of large-size is brilliant by interspersed assembling；CNA-2 samples are rule and grain Spend the spherical structure of narrow distribution, CNA-2 particle size is smaller, be 0.6 ± 0.2 μm, CNA-2 samples rough and There are many little particles raised, formed by the cuprous nano of reduced size is brilliant by self assembly in order in situ；Cuprous oxide is produced Thing is nanometer crystal assembly structure.
Compared with prior art, its preparation technology is simple by the present invention, and principle is reliable, and preparation cost is low, and product purity is high, electricity Magnetic performance is good, is widely used, and use environment is friendly.
Brief description of the drawings：
(a) CNA-1 and (b) CNA-2 X-ray diffractogram that Fig. 1 is prepared for the present invention.
(a, c) CNA-1 and (b, d) CNA-2 scanning electron microscope diagram that Fig. 2 is prepared for the present invention.
Fig. 3 is (A) CNA-1 for preparing of the present invention and (B) CNA-2 nitrogen adsorption/desorption curve, (C) CNA-1 and (D) CNA-2 BJH pore size distribution curves.
(a) CNA-1 and (b) CNA-2 magnetic hysteresis curve (A) that Fig. 4 is prepared for the present invention, (B) is put for the part of figure (A) Big figure.
(a) CNA-1/GCE and (b) CNA-2/GCE that Fig. 5 is prepared for the present invention in AA, DA and UA electrolyte is contained respectively Cyclic voltammetry curve.
(a) CNA-1/GCE and (b) CNA-2/GCE that Fig. 6 is prepared for the present invention contain AA (1mmol/L), DA at the same time Differential pulse voltammetry curve in (0.8mmol/L) and UA (1mmol/L) electrolyte.
(A) CNA-1/GCE and (B) CNA-2/GCE that Fig. 7 is prepared for the present invention are 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 is composed 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.
(a) CNA-1/GCE and (b) CNA-2/GCE that Figure 10 is prepared for the present invention are 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 below by embodiment and with reference to accompanying drawing.
Embodiment：
(1) prepared by the brilliant assembly of cuprous nano：
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, add 15mL 0.9mmol ascorbic acid solution, keep 1h is stirred under identical heating-up temperature；Then three-necked flask, which is removed, 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, plus 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 ° Diffraction maximum with 73.69 ° of appearance is corresponding with (110), (111), (200), (220) and (311) face that pure zirconia is cuprous respectively, Show that obtained sediment sample is cuprous oxide, and without any impurity；Diffraction maximum in analysis chart 1 can be obtained, CNA-2's Most strong diffraction maximum ((111) face) is wider, and the diffraction maximum in CNA-1 (111) face point and it is narrow, illustrate crystallization nanocrystalline in CNA-1 Size is than larger；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, from Fig. 2 a, and 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 finds that CNA-2 particle size is smaller, is 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 of reduced size is brilliant 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 it is meso-hole structure to show the cuprous oxide synthesized by the system, and the result is sub- for oxidation The structure determination of copper nanocrystallite assembly, which is provided, to be supported；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；
(2) magnetic performance of the brilliant assembly of cuprous nano is determined：
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；
(3) preparation of modified electrode：
The suspension for being 1.5mg/mL with the brilliant assembly configuration concentration of secondary water and cuprous nano, it is dispersed after take 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；
(4) electrocatalysis characteristic of cuprous oxide modified electrode is determined：
Fig. 5 utilizes two kinds of cuprous oxide assembly modified electrode Ascorbic Acids (AA) of cyclic voltammetric technique study, many 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；In comparison diagram 5a and b, 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 CNA-2/GCE can in the case where ascorbic acid, three kinds of biomolecule of dopamine and uric acid coexist DA and UA is 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 Flow valuve is with the substantially linear increase of the increase of DA concentration, and 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, CNA-2/GCE in three kinds of mixed liquors to DA detection than CNA-1/GCE possess preferably selectivity and Higher sensitivity；
(5) absorption property of cuprous oxide modified electrode is determined：
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 the brilliant assembly of prepared cuprous nano；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 be mainly is adsorbed onto on the brilliant assembly of cuprous nano by suction-operated；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；Have smaller cuprous nano brilliant in CNA-2 and its special package assembly institute Caused by the loose structure of formation；
(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 a speed limit electro transfer and adsorption of oxygen formation cuprous oxide superoxides (formula 8-1) process, 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 the brilliant assembly of cuprous nano potential catalysis to live to oxygen reduction Property；
Cu2O-O2+e-→Cu2O-O2 - (1)
Cu2O-O2+H2O+e-→Cu2O-HO2+OH- (2)。

Claims (1)

1. a kind of preparation method of the brilliant assembly of cuprous nano, it is characterised in that：By low temperature liquid phase synthetic technology scheme, With the principle of the cuprous presoma of ascorbic acid reduction-oxidation, the brilliant assembly of two kinds of various sizes of cuprous nanos is prepared；Will The ammonium bicarbonate aqueous solution that the copper sulphate and 30ml concentration that 120ml concentration is 3mmol are 6mmol is well mixed in three-necked flask After be heated with stirring to 45-50 DEG C keep 20 minutes, add 45mmol aqueous ascorbic acids reduction, reduction reaction is after 60 minutes Collect sediment；Carry out after centrifuge washing 50-60 DEG C of temperature control to sediment with deionized water again and dry, collect sediment name For CNA-1；Copper sulphate in above-mentioned steps is changed to concentration for 3mmol copper acetates again, ammonium bicarbonate concentration is 12mmol and anti-bad Hematic acid concentration of aqueous solution is 45mmol, and the agitating and heating time is 90 minutes after being well mixed in three-necked flask, using identical The sediment that preparation flow is obtained is named as CNA-2；The brilliant assembly of the cuprous nano of preparation includes two kinds of physical dimensions, point CNA-1 and CNA-2 are not named as, wherein, CNA-1 is irregular micro-meter scale flowers shape structure, and size is 1.8 ± 0.3 μm, by Crystal size is formed for 32nm cuprous nano crystal grain by interspersed assembling；CNA-2 is regular and narrower particle size distribution Spherical structure, size is 0.6 ± 0.2 μm, is passed through by crystal size for 10nm cuprous nano crystal grain in situ orderly from group Dress is formed, and CNA-2 is rough and has particle raised；CNA-1 and CNA-2 saturation magnetizations be 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, catalysis oxygen also Original reaction；Its physical dimension is inversely proportional with electro-catalysis selectivity, adsorption capacity and electro-catalysis ability；For Multifunction Sensor Nano material.
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