A kind of ZnO polycrystal nanobelt package assembly of high H2-producing capacity atomic state Ag modification
Preparation method
Technical field
The invention belongs to catalysis material and its preparation technical fields, and in particular to high H2-producing capacity atomic state Ag modification
The preparation method of ZnO polycrystal nanobelt package assembly.
Background technique
Photocatalitic Technique of Semiconductor is with the chemical conversion of solar energy and to be stored as core, by converting solar energy into hydrogen
The photolysis water hydrogen technology of energy, is expected to thoroughly solve the problems, such as that fossil energy exhaustion and greenhouse effects are brought.Due to this photochemical
Method, which can be used directly to decompose water, generates hydrogen, the alleviating energy crisis the problems such as in terms of great attention by people.
Currently, photocatalysis technology has been developing progressively as emerging frontier in chemistry subject, still, the key of technology development
And key problem is still to study to visible light-responded effective, efficient and cheap photochemical catalyst.
Zinc oxide (ZnO) is a kind of broad stopband (3.2eV) direct band-gap semicondictor, but ZnO quantum efficiency is low and excites
The short limitation of wavelength, can not be widely applied, and in order to overcome these, be modified to ZnO.Noble metal (Au, Pt, Ag)/ZnO nano
Structure obtains the extensive research of researcher due to its excellent photocatalytic activity.In these noble metals, Ag nanoparticle due to
Its excellent chemical stability and high electron conductivity play an important role during capturing light induced electron.Ag load
On the surface of metal oxide, it can effectively enhance the charge-transfer dynamics between metal and interface.Although at present
There is more synthetic strategy preparation Ag/ZnO composite material, but the ZnO nano-structure for loading atomic state Ag is not reported, this hair
It is bright that the atomic state Ag of high dispersive is introduced into the crystal boundary of ZnO polycrystal nanobelt using liquid phase reactor and low temperature calcination method, it obtains
The ZnO polycrystal nanobelt package assembly of atomic state Ag modification.This nanobelt package assembly is used for simulated solar irradiation photocatalytic water system
Hydrogen, photostability is high, and hydrogen production efficiency is greatly improved than pure ZnO nano-structure.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of by atomic state Ag, and to be introduced into ZnO more
In brilliant nanobelt crystal boundary, nanobelt package assembly is prepared, simple process, mild condition greatly reduce the load of precious metals ag
Amount, it is at low cost, can industrialized production, and no pollution to the environment.The ZnO nano-band package assembly tool of obtained atomic state Ag modification
There is high H2-producing capacity.
To achieve the goals above, the technical solution adopted by the present invention is as follows: a kind of high H2-producing capacity Ag/ZnO nanobelt
The preparation method of package assembly, comprising the following steps:
(1) the acetic acid dihydrate zinc of 0.01~0.5mol/L is dissolved in deionized water, obtains clear solution A;
(2) hexamethylenetetramine of 0.01~0.5mol/L and urea are dissolved in deionized water in proportion, and are transferred to step
(3) in the clear solution A obtained, clear solution B is obtained
(3) silver nitrate solution of certain volume is added in the clear solution B that step (2) obtain, is stirred evenly;
(4) will the solution that prepared in step (3) move into reactor in, be put in after sealing 6~100 DEG C reaction 3~for 24 hours after it is cold
But;
(5) after step (4), obtained product is centrifuged, and will the obtained product deionized water of centrifugation and anhydrous
Ethanol washing is for several times, dry, and the solid tubular type kiln roasting after drying obtains high H2-producing capacity Ag/ZnO nanobelt package assembly
Finished product.
The present invention, in step (2), the molar ratio of hexamethylenetetramine and urea is 1:1~1:50.
The present invention, in step (3), the silver nitrate solution of certain volume is mole according to acetic acid dihydrate zinc and silver nitrate
Than what is converted for 1000:1~100:1.
The present invention, in step (4), reaction temperature is 70~100 DEG C, reaction time range is 3~for 24 hours.
The present invention, in step (5), maturing temperature is 200~300 DEG C, 0.5~2h of calcining time.
Preparation method of the present invention is easy to operate, and preparation cost is low, can be mass-produced, gained atomic state Ag modification
ZnO polycrystal nanobelt package assembly, regular appearance, size adjustable have preferable crystal form;In addition, being modified by atomic state Ag
ZnO polycrystal nanobelt package assembly can widen ZnO nano material in visible region absorption region, improve photocatalytic activity;
For the ZnO polycrystal nanobelt package assembly of atomic state Ag modification for photolysis water hydrogen under simulated solar irradiation, hydrogen generation efficiency is up to 325
μmol·h-1·g-1, it is 4 times of pure ZnO.
Detailed description of the invention
Fig. 1 is the SEM photograph for the ZnO polycrystal nanobelt package assembly that atomic state Ag modification is made in embodiment 1 (AZ-1);
Fig. 2 is the ZnO polycrystal nanobelt package assembly and comparative example preparation of the atomic state Ag modification of embodiment 1-3 preparation
Pure ZnO photocatalyst simulated solar irradiation irradiation under production hydrogen curve.
Specific embodiment
Below by way of preferred embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited to
This.
Embodiment 1
It weighs 0.06mol/L acetic acid dihydrate zinc to be dissolved in deionized water, obtains clear solution A;Weigh 0.036mol/L
Hexamethylenetetramine and 0.8mol/L urea are dissolved in deionized water, obtain clear solution B;Solution B is added in solution A,
The silver nitrate solution of 5mL is added in mixed solution, is uniformly mixed and obtains reaction system, mixed liquor is moved into reaction vessels,
After reacting 12h in 90 DEG C of baking ovens, centrifugation, washing, the solid after drying is in tubular type kiln roasting, and maturing temperature is 300 DEG C, heat preservation
After half an hour, finished product is obtained.
Embodiment 2
It weighs 0.06mol/L acetic acid dihydrate zinc to be dissolved in deionized water, obtains clear solution A;Weigh 0.036mol/L
Hexamethylenetetramine and 0.3mol/L urea are dissolved in deionized water, obtain clear solution B;Solution B is added in solution A,
The silver nitrate solution of 5mL is added in mixed solution, is uniformly mixed and obtains reaction system, mixed liquor is moved into reaction vessels,
After reacting 12h in 90 DEG C of baking ovens, centrifugation, washing, the solid after drying 300 DEG C of maturing temperature, keep the temperature half in tubular type kiln roasting
After a hour, finished product is obtained.
Embodiment 3
It weighs 0.06mol/L acetic acid dihydrate zinc to be dissolved in deionized water, obtains clear solution A;Weigh 0.036mol/L
Hexamethylenetetramine and 1.6mol/L urea are dissolved in deionized water, obtain clear solution B;Solution B is added in solution A,
The silver nitrate solution of 5mL is added in mixed solution, is uniformly mixed and obtains reaction system, mixed liquor is moved into reaction vessels,
After reacting 12h in 90 DEG C of baking ovens, centrifugation, washing, the solid after drying is in tubular type kiln roasting, and maturing temperature is 300 DEG C, heat preservation
After half an hour, finished product is obtained.
Embodiment 4
It weighs 0.12mol/L acetic acid dihydrate zinc to be dissolved in deionized water, obtains clear solution A;Weigh 0.072mol/L
Hexamethylenetetramine and 1.6mol/L urea are dissolved in deionized water, obtain clear solution B;Solution B is added in solution A,
The silver nitrate solution of 5mL is added in mixed solution, is uniformly mixed and obtains reaction system, mixed liquor is moved into reaction vessels,
After reacting 6h in 90 DEG C of baking ovens, centrifugation, washing, the solid after drying is in tubular type kiln roasting, and maturing temperature is 300 DEG C, heat preservation
After half an hour, finished product is obtained.
Embodiment 5
It weighs 0.12mol/L acetic acid dihydrate zinc to be dissolved in deionized water, obtains clear solution A;Weigh 0.072mol/L
Hexamethylenetetramine and 0.8mol/L urea are dissolved in deionized water, obtain clear solution B;Solution B is added in solution A,
The silver nitrate solution of 5mL is added in mixed solution, is uniformly mixed and obtains reaction system, mixed liquor is moved into reaction vessels,
After reacting 12h in 80 DEG C of baking ovens, centrifugation, washing, the solid after drying is in tubular type kiln roasting, and maturing temperature is 300 DEG C, heat preservation
After half an hour, finished product is obtained.
Comparative example
It weighs 0.06mol/L acetic acid dihydrate zinc to be dissolved in deionized water, obtains clear solution A;Weigh 0.036mol/L
Hexamethylenetetramine and 0.8mol/L urea are dissolved in deionized water, obtain clear solution B;Solution B is added in solution A, is mixed
Conjunction uniformly obtains reaction system, and mixed liquor is moved into reaction vessels, and after reacting 12h in 90 DEG C of baking ovens, centrifugation, washing are done
For solid after dry in tubular type kiln roasting, maturing temperature is 300 DEG C, after keeping the temperature half an hour, obtains finished product
Using the pattern of scanning electron microscope (SEM) observation product, the original that can be seen that from the photo in Fig. 1
The ZnO polycrystal nanobelt package assembly of sub- state Ag modification is the microballoon assembled by nanobelt, and the length of nanobelt is about 10 μ
m.The light of the ZnO polycrystal nanobelt package assembly of gained atomic state Ag modification is evaluated using CEL-SPH2N photocatalysis evaluation system
Water hydrogen manufacturing performance is solved, the ZnO polycrystalline of atomic state Ag modification is received it can be seen from the production hydrogen curve under the irradiation of Fig. 2 simulated solar irradiation
Rice band package assembly is for photolysis water hydrogen under simulated solar irradiation, hence it is evident that better than the pure ZnO of comparative example preparation, hydrogen generation efficiency can be with
Up to 325 μm of olh-1·g-1, it is 4 times of pure ZnO.