CN105233876B - The technique that one-step method prepares porphyrin functionalized nano copper sulfide - Google Patents
The technique that one-step method prepares porphyrin functionalized nano copper sulfide Download PDFInfo
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- CN105233876B CN105233876B CN201510237338.3A CN201510237338A CN105233876B CN 105233876 B CN105233876 B CN 105233876B CN 201510237338 A CN201510237338 A CN 201510237338A CN 105233876 B CN105233876 B CN 105233876B
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- porphyrin
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Abstract
The invention discloses the technique that one-step method prepares porphyrin functionalized nano copper sulfide, step is as follows：Tetracarboxylic phenyl porphyrin is completely dissolved in the sodium hydroxide solution that pH is 89, the pH value for adjusting above-mentioned solution with a small amount of certain density hydrochloric acid solution is 67；Water-soluble zinc salt solution is prepared, is added in above-mentioned solution, is well mixed, obtains solution A；Then hydrochloric acid solution is added in a certain amount of thioacetamide and obtains solution B；Solution A and solution B are placed in the molten device of sealing simultaneously, reacted 12 24 hours under the conditions of being stirred at room temperature, then scrubbed drying obtains the nano-copper sulfide complex of porphyrin functionalization.Compared with prior art, this method has that preparation technology is simple, easy to operate, cost is low, and porphyrin consumption is few, reaction condition gentle and the advantages of high income；Have the advantages that purity height, size are small, active good using the nanometer sulfide of porphyrin functionalization made from this method.
Description
Technical field
The technique that the nano-copper sulfide of porphyrin functionalization is prepared the present invention relates to one-step method, belongs to the system of nano composite material
Standby technical field.
Background technology
In inorganic nano semiconductor, nano metal sulfide material is due to its special architectural feature and is widely applied
Prospect so that nano metal sulfide material turns into the another important research field of new inorganic semiconductor, has attracted more and more
Researcher concern.
In optoelectronic areas, luminosity that metal sulfide has due to it, nonlinear optical property, photocatalysis,
Light conversion properties matter etc., is widely used in various solar cells, laser and infrared probe device, electroluminescent device, ultraviolet
Optical sensor etc..Such as ZnS is because it has higher transmitance in 3-5 μm and 8-12 μm infrared band of visible ray and turns into laser
The excellent infrared viewing window of device and aircraft【It is foolish brave, Zheng Xiulin, the positive hall Journal of Inorganic Materials of Liu, 1997,12 (3):346-
350.】。
In terms of catalysis, due to the peculiar property of nano material, metal sulfide is widely used as catalyst.Such as CdS
Because its less energy gap can absorb more visible ray and directly apply to the photocatalytic degradation and work of organic dyestuff
In terms of sensitising agent for TiO2 Photodegradation catalysts【Xiangqing Li,Lifang Liu,Shi-Zhao Kang,Jin
Mu,Guodong Li,Catalysis Communications 17(2012)136–139】, and there are some researches show CdS performances
Go out the activity and Mimetic enzyme of peroxidase activity of good photocatalytically degradating organic dye.In petrochemistry field, reduction
Raney nickel cure after, the catalyst to diethyl olefin hydrogenation generate monoolefine reaction have selectivity.
Easy absorption yet with single nano material, the shortcoming easily assembled, cause the reduction of its chemism point, so that
Cause its active reduction.In order to overcome this defect, researchers have turned to sight in the modification to metal sulfide.Example
Such as, chitosan/Nano cadmium sulphide compound features have gone out the Congo red effect of higher preferably visible light photocatalytic degradation.
Porphyrin is as the derivative of porphines, the big pi bond with the electronics of 24 center 26.Porphyrin Molecule surface is larger and tool is firm
Property, the features such as possessing wide and height the chemical stability of electronics resiliency, photoelectric magnetic property, spectral response and light sensitivity, so that
Porphyrin is set to be had a wide range of applications in terms of Solar use, analysis detection, catalysis, biochemistry and sensing.
The content of the invention
For the disadvantages mentioned above present in metal sulfide, there is provided one kind with porphyrin modified metal sulfide by the present invention
The technique that one-step method prepares porphyrin functionalized nano copper sulfide.
The adopted technical solution is that：
One-step method prepares the technique of porphyrin functionalized nano copper sulfide, comprises the following steps：
(1) selection tetracarboxylic phenyl porphyrin, water-soluble metal salt, thioacetamide and hydrochloric acid are raw material；
(2) tetracarboxylic phenyl porphyrin is dissolved in the sodium hydroxide solution that pH value is 8, above-mentioned solution is adjusted with hydrochloric acid solution
PH value be 6-7；
(3) water-soluble metal salting liquid is prepared, is added in above-mentioned solution, is well mixed, obtains solution A；
(4) hydrochloric acid solution is added in thioacetamide, obtains solution B；
(5) solution A and solution B are placed in sealing container simultaneously, reaction 12-24 hours under the conditions of being stirred at room temperature, so
By washing drying, porphyrin functionalized nano sulfide is made.
In step (1)：The water-soluble metal salt preferably water miscible cadmium salt, zinc salt or mantoquita.The water miscible cadmium
The preferred caddy of salt or cadmium nitrate；The preferred zinc nitrate of water miscible zinc salt or zinc acetate；The water miscible mantoquita is preferred
Copper chloride.
In step (1)：The mol ratio of the tetracarboxylic phenyl porphyrin and water-soluble metal salt is preferably 1: 400~1:
4000。
In step (1)：The concentration of hydrochloric acid solution is preferably 0.1-1mol/L.
In step (4)：Described water-soluble metal salt and the mol ratio of thioacetamide are preferably 1: 5~1: 25.
In step (4)：The mol ratio of the hydrochloric acid and thioacetamide is preferably greater than 1.2.
In step (5)：Drying temperature is preferably 60-70 DEG C.
In step (5)：The sealing container can be hermetically drying device or sealing retort etc..
The method have the benefit that：
Compared with prior art, the present invention uses porphyrin modified metal sulfide, the nanometer of obtained porphyrin functionalization
Sulfide particles have the advantages that purity height, size are small, active good, with preferable photocatalytic activity and class peroxidase activity
Property；Product is made using one-step method in the present invention in addition, and this method has that preparation technology is simple, easy to operate, cost is low, and porphyrin is used
Amount less, reaction condition gentle and the advantages of high income.
Brief description of the drawings
The invention will be further described with embodiment below in conjunction with the accompanying drawings：
Fig. 1 is the X-ray diffractogram of the cadmium sulfide nano-particles of porphyrin functionalization made from embodiment 1；
Fig. 2 is the transmission electron microscope picture of the cadmium sulfide nano-particles of porphyrin functionalization made from embodiment 1；
Fig. 3 is the X-ray diffractogram of the Zinc sulfide nano-particle of porphyrin functionalization made from embodiment 2；
Fig. 4 is the transmission electron microscope picture of the Zinc sulfide nano-particle of porphyrin functionalization made from embodiment 2；
Degradation rate and the relation curve of time when Fig. 5 is Photocatalytic Degradation Property test experiments.
Embodiment
Embodiment 1
Weigh 1mg tetracarboxylic phenyl porphyrins to be placed in beaker, adding 10ml pH=8 sodium hydroxide solution makes its complete
Dissolving, forms deep purple solution, and the hydrochloric acid solution for being then 0.5mol/L with a small amount of concentration adjusts above-mentioned solution to pH=6.Claim
Take 0.9166g (0.005mol) solid chlorine cadmium to be dissolved in 5ml water, the cadmium chloride solution prepared is added to above-mentioned solution
In and be well mixed, obtain solution A.250ml concentration is added to 7.513g's (0.1mol) for 0.5mol/L hydrochloric acid solution
Solution B is formed in thioacetamide.Then solution A and solution B are placed in hermetically drying device simultaneously, under the conditions of being stirred at room temperature
Reaction 24 hours.Reaction collects yellow mercury oxide after terminating, and uses ultra-pure water centrifuge washing, and obtain within 12 hours in drying at 60 DEG C
The Nano cadmium sulphide of porphyrin functionalization.The cadmium sulfide nano-particles product purity of porphyrin functionalization is 100%, and yield is
91.2%.The product of gained is characterized, as shown in Figure 1 and Figure 2.From figure 1 it appears that the peak in collection of illustrative plates is both corresponded to
The diffraction maximum of cadmium sulfide, and without other miscellaneous peaks, it is pure cadmium sulfide thus to prove products obtained therefrom；From the transmission shown in Fig. 2
It can be seen that products obtained therefrom is nano-particle in electromicroscopic photograph, the size of nano-particle is 20-50nm.
Embodiment 2
Weigh 1mg tetracarboxylic phenyl porphyrins to be placed in beaker, adding 10ml pH=8 sodium hydroxide solution makes its complete
Dissolving, forms deep purple solution, and the hydrochloric acid solution for being then 0.5mol/L with a small amount of concentration adjusts above-mentioned solution to pH=6.Claim
Take 0.3658g (0.0017mol) solid zinc acetate to be dissolved in 5ml water, the zinc acetate solution prepared is added to above-mentioned molten
In liquid and it is well mixed, obtains solution A.80ml concentration is added to 2.504g for 0.5mol/L hydrochloric acid solution
Solution B is formed in the thioacetamide of (0.0333mol).Then solution A and solution B are placed in hermetically drying device simultaneously, in
Reacted 24 hours under the conditions of being stirred at room temperature.Reaction collects sediment after terminating, and uses ultra-pure water centrifuge washing, and in dry at 60 DEG C
The nano-zinc sulfide for obtaining porphyrin functionalization in 12 hours.The Zinc sulfide nano-particle product purity of porphyrin functionalization is 100%, is received
Rate is 90.5%.The product of gained is characterized, as shown in Figure 3,4, as seen from Figure 3, the peak in collection of illustrative plates is both corresponded to
The diffraction maximum of zinc sulphide, and without other miscellaneous peaks, it is pure zinc sulphide thus to prove products obtained therefrom；From the transmission shown in Fig. 4
It can be seen that products obtained therefrom is nano-particle in electromicroscopic photograph, nano particle diameter is than more uniform, and size is 10nm or so.
Embodiment 3
Weigh 6mg tetracarboxylic phenyl porphyrins to be placed in beaker, adding 10ml pH=8 sodium hydroxide solution makes its complete
Dissolving, forms deep purple solution, and the hydrochloric acid solution for being then 0.5mol/L with a small amount of concentration adjusts the pH=6 of above-mentioned solution.Claim
Take 0.8524g (0.005mol) solid chlorine copper to be dissolved in 5ml water, the copper chloride solution prepared is added to above-mentioned solution
In and be well mixed, obtain solution A.180ml concentration is added to 4.6765g's (0.0622mol) for 0.5mol/L hydrochloric acid
Solution B is formed in thioacetamide.Then solution A and solution B are placed in hermetically drying device simultaneously, under the conditions of being stirred at room temperature
Reaction 24 hours.Reaction collects sediment after terminating, and uses ultra-pure water centrifuge washing, and obtain porphyrin within 12 hours in drying at 60 DEG C
The nano-copper sulfide product of functionalization.
Embodiment 4
Weigh 4.2mg tetracarboxylic phenyl porphyrins to be placed in beaker, adding 10ml pH=9 sodium hydroxide solution makes its complete
Fully dissolved, forms deep purple solution, and the hydrochloric acid solution for being then 0.5mol/L with a small amount of concentration adjusts above-mentioned solution to pH=
6.5.The solid chlorine cadmium for weighing 0.3666g (0.002mol) is dissolved in 5ml water, and the cadmium chloride solution prepared is added to
State in solution and be well mixed, obtain solution A.50ml concentration is added to 1.1269g for 0.5mol/L hydrochloric acid solution
Solution B is formed in the thioacetamide of (0.015mol).Then solution A and solution B are placed in hermetically drying device simultaneously, in room
Reacted 18 hours under warm stirring condition.Reaction collects sediment after terminating, and uses ultra-pure water centrifuge washing, and at 60 DEG C dry 12
Hour obtains the Nano cadmium sulphide of porphyrin functionalization.The cadmium sulfide nano-particles product purity of porphyrin functionalization is 100%.
Embodiment 5
Weigh 4mg tetracarboxylic phenyl porphyrins to be placed in beaker, adding 10ml pH=8 sodium hydroxide solution makes its complete
Dissolving, forms deep purple solution, and the hydrochloric acid solution for being then 0.3mol/L with a small amount of concentration adjusts above-mentioned solution to pH=6.Claim
Take 0.9166g (0.005mol) solid chlorine cadmium to be dissolved in 5ml water, the cadmium chloride solution prepared is added to above-mentioned solution
In and be well mixed, obtain solution A.450ml concentration is added to 3.7565g (0.05mol) for 0.3mol/L hydrochloric acid solution
Thioacetamide in form solution B.Then solution A and solution B are placed in hermetically drying device simultaneously, condition is stirred at room temperature
Lower reaction 20 hours.Reaction collects sediment after terminating, and uses ultra-pure water centrifuge washing, and obtain porphin within 10 hours in drying at 60 DEG C
The nano-zinc sulfide of quinoline functionalization.The Zinc sulfide nano-particle product purity of porphyrin functionalization is 100%.
Tetracarboxylic phenyl porphyrin full name mentioned in the present invention is 5,10,15,20- tetra- (4- carboxyl phenyls) porphyrins, point
Son amount is 790.79, and structural formula is as follows：
Photocatalytic Degradation Property is tested：
1. preparation mass concentration is 4mg/L rhodamine B 40ml in 100ml beaker；
2. the cadmium sulfide nano-particles for weighing porphyrin functionalization prepared in 40mg embodiments 1 are added in above-mentioned solution,
Ultrasound is uniform and continues stirring；
It is irradiated 3. solution is placed under sunshine, 3ml solution is taken out at different time interval, centrifuges, take supernatant
Liquid surveys its absorbance；
4. its photocatalytic degradation efficiency is calculated, degradation rate and the effect such as Fig. 5 that fades.
Interpretation of result：Under sunshine irradiation, rhodamine B solution is significantly degraded in experiment, and degradation rate reaches within 2 hours
More than 90 percent, color also gradually becomes colourless by pink, fades obvious.Experiment shows the porphyrin prepared by the present invention
The sulfide nano-material of functionalization has good Photocatalytic activity in visible region, being capable of catalytic degradation water well
Harmful dyestuff (rhodamine B) in body and other environment, has application value well in terms of water process.
Claims (4)
1. the technique that one-step method prepares porphyrin functionalized nano copper sulfide, it is characterised in that comprise the following steps：
(1) selection tetracarboxylic phenyl porphyrin, water-soluble metal salt, thioacetamide and hydrochloric acid are raw material；
(2) tetracarboxylic phenyl porphyrin is dissolved in the sodium hydroxide solution that pH value is 8, the pH of above-mentioned solution is adjusted with hydrochloric acid solution
It is worth for 6-7；
(3) water-soluble metal salting liquid is prepared, is added in above-mentioned solution, is well mixed, obtains solution A；
(4) hydrochloric acid solution is added in thioacetamide, obtains solution B；
(5) solution A and solution B are placed in sealing container simultaneously, reacted 12-24 hours under the conditions of being stirred at room temperature, Ran Houxi
Drying is washed, porphyrin functionalized nano copper sulfide is made；
Described water-soluble metal salt and the mol ratio of thioacetamide are 1: 5~1: 25；The water-soluble metal salt is water
The mantoquita of dissolubility；
In step (1)：The mol ratio of tetracarboxylic phenyl porphyrin and water-soluble metal salt is 1: 400~1: 4000, concentration of hydrochloric acid
For 0.1-1mol/L；
In step (4)：The mol ratio of the hydrochloric acid and thioacetamide is more than 1.2；
The tetracarboxylic phenyl porphyrin is 5,10,15,20- tetra- (4- carboxyl phenyls) porphyrin.
2. the technique that one-step method according to claim 1 prepares porphyrin functionalized nano copper sulfide, it is characterised in that described
Water miscible mantoquita is copper chloride.
3. the technique that one-step method according to claim 1 prepares porphyrin functionalized nano copper sulfide, it is characterised in that step
(5) in：Drying temperature is 60-70 DEG C.
4. the technique that one-step method according to claim 1 prepares porphyrin functionalized nano copper sulfide, it is characterised in that step
(5) in：The sealing container is hermetically drying device or sealing retort.
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| CN201310547329.5A CN103586084B (en) | 2013-11-07 | 2013-11-07 | Process for preparing porphyrin-functionalized nano sulfide with one-step method |
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| CN201510237256.9A Expired - Fee Related CN105233874B (en) | 2013-11-07 | 2013-11-07 | The technique that one-step method prepares porphyrin functionalized nano zinc sulphide |
| CN201510237338.3A Expired - Fee Related CN105233876B (en) | 2013-11-07 | 2013-11-07 | The technique that one-step method prepares porphyrin functionalized nano copper sulfide |
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| CN201510237256.9A Expired - Fee Related CN105233874B (en) | 2013-11-07 | 2013-11-07 | The technique that one-step method prepares porphyrin functionalized nano zinc sulphide |
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| CN105312066A (en) * | 2015-05-12 | 2016-02-10 | 山东科技大学 | Preparing method for zinc sulfide-montmorillonite nanometer composite material |
| CN105536874A (en) * | 2015-12-15 | 2016-05-04 | 山东科技大学 | Method for preparing double-layer porphyrin-phthalocyanine cerium functionalized nanometer cadmium sulfide on interface |
| CN106076420B (en) * | 2016-06-08 | 2018-10-23 | 广西大学 | The preparation method and application of cadmium sulfide immobilized four (4- carboxyl phenyls) ferriporphyrin catalysis material |
| CN107176958B (en) * | 2017-06-01 | 2019-05-24 | 熊子达 | 5 with nanostructure, 10,15,20- tetra- (4- carboxyl phenyl) porphyrins and preparation method thereof |
| CN107759803B (en) * | 2017-11-13 | 2020-07-03 | 山东师范大学 | Tetrasulfhydryl porphyrin compound and preparation method and application thereof |
| CN108586469B (en) * | 2018-03-19 | 2021-05-07 | 西北师范大学 | Method for inhibiting photo-corrosion of cadmium sulfide |
| CN109239143B (en) * | 2018-09-17 | 2020-09-29 | 浙江理工大学 | Preparation method of nano-copper modified metalloporphyrin nanotube-cadmium sulfide nanosheet composite photosensitive sensing material |
| CN109433176A (en) * | 2018-11-07 | 2019-03-08 | 山东科技大学 | A kind of titanium dioxide-montmorillonite nanometer complex preparation method of porphyrin functionalization |
| CN113150559B (en) * | 2021-05-20 | 2023-02-07 | 潍坊学院 | Copper sulfide anchored porphyrin-based porous organic polymer and dual-signal electrochemical biosensor |
| CN115368579B (en) * | 2022-07-05 | 2023-06-27 | 南京大学 | Preparation method and application of nano-enzyme with manganese porphyrin as metal organic framework |
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| CN102568852A (en) * | 2012-01-20 | 2012-07-11 | 中国科学院上海硅酸盐研究所 | Photovoltaic cell based on three-dimensional graphene and preparation method thereof |
| CN102921463A (en) * | 2012-10-12 | 2013-02-13 | 广西大学 | Nano zinc sulfide metalloporphyrin catalyst and preparation method and application thereof |
| CN103159771A (en) * | 2013-03-29 | 2013-06-19 | 山东科技大学 | Technique for synthesizing porphyrin-functionalized cobalt oxide nanoparticles by one-step method |
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| BRPI0722353A2 (en) * | 2007-12-28 | 2014-03-18 | Univ Aix Marseille Ii | HYBRID NANOCOMPOSITS |
| GB201009969D0 (en) * | 2010-06-15 | 2010-07-21 | Ecosynth Bvba | Transesterification process using mixed salt acetylacetonates catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102568852A (en) * | 2012-01-20 | 2012-07-11 | 中国科学院上海硅酸盐研究所 | Photovoltaic cell based on three-dimensional graphene and preparation method thereof |
| CN102921463A (en) * | 2012-10-12 | 2013-02-13 | 广西大学 | Nano zinc sulfide metalloporphyrin catalyst and preparation method and application thereof |
| CN103159771A (en) * | 2013-03-29 | 2013-06-19 | 山东科技大学 | Technique for synthesizing porphyrin-functionalized cobalt oxide nanoparticles by one-step method |
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| CN103586084A (en) | 2014-02-19 |
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| CN105233874A (en) | 2016-01-13 |
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