CN105148925A - Three-dimensional ordered macroporous ZnO-Cu2O-TiO2 composite oxide with regulatable oxygen vacancy as well as preparation method and application of composite oxide - Google Patents

Three-dimensional ordered macroporous ZnO-Cu2O-TiO2 composite oxide with regulatable oxygen vacancy as well as preparation method and application of composite oxide Download PDF

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CN105148925A
CN105148925A CN201510655386.4A CN201510655386A CN105148925A CN 105148925 A CN105148925 A CN 105148925A CN 201510655386 A CN201510655386 A CN 201510655386A CN 105148925 A CN105148925 A CN 105148925A
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CN105148925B (en
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杨仁春
卢小佳
刘琪
张欢
朱玲婷
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Anhui Polytechnic University
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Abstract

The invention provides a three-dimensional ordered macroporous ZnO-Cu2O-TiO2 composite oxide with a regulatable oxygen vacancy, as well as a preparation method and application of the composite oxide. Compared with the prior art, the preparation method provided by the invention has the advantages that ethylene glycol is taken as a solvent, so that the formation rate of a colloid can be effectively controlled, and the control of the formation rate of the colloid and preparation of the ZnO-Cu2O-TiO2 composite oxide can be realized without adding any acid-alkali regulating agents; meanwhile, a situation of joint oxygen consumption by copper ions and zinc ions is formed according to the variable valence state of the copper ions, so that the concentration of the oxygen vacancy in the composite oxide can be conveniently regulated by adjusting the substance ratio of copper nitrate to zinc nitrate, and the photocatalytic performance of the ZnO-Cu2O-TiO2 composite oxide can be improved.

Description

The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2composite oxides, preparation method and application thereof
Technical field
The invention belongs to Photocatalysis Function Material field, be specifically related to the three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2composite oxides, preparation method and application thereof.
Background technology
Semi-conducting material, because it has special electronic structure, illustrates significant development potentiality in the field such as the energy, environment, is subject to extensive concern.Among numerous semi-conducting materials, titanium oxide has the characteristics such as green non-poisonous, cheap, stable in properties because of it, is one of semi-conducting material of greatest concern.
As everyone knows, titanium dioxide has special performance in optical, electrical, magnetic etc., is particularly used widely in fields such as new forms of energy, the photocatalysis depollution of environment, sensings, therefore it has immeasurable research and development and to be worth and market is applied.
As catalysis material, its chemical composition, microstructure are very remarkable on the impact of its catalytic performance.Recent studies have shown that, introduce doped chemical in a semiconductor material, can promote that it has the generation of the Lacking oxygen of significantly impact on photocatalysis, the Lacking oxygen of semiconductor catalysis material is on its catalytic performance impact very significantly (Science, 2011,331 (6018): 746-750), often compared with its one-component semi-conducting material, there is more excellent process based prediction model.
At present, construct Lacking oxygen many employings high temperature reduction or quenching technology, operating process is not only complicated but also cost is high.Although existing relevant report is taked doping method can realize Lacking oxygen to construct, due to high-temperature roasting condition, to TiO in recent years 2doping often mainly with cupric (CuO) form exist, obviously, divalent copper oxides (CuO) does not have remarkable photoresponse effect, obviously unfavorable to photocatalysis.From reporting at present, adopt monovalence cuprous oxide (Cu 2and the ZnO-Cu of zinc oxide (ZnO) original position codope O) 2o-TiO 2composite oxides preparation have not been reported.Meanwhile, porous TiO more prevailing at present 2mostly preparation method is the sol-gel process regulated and controled by pH.But, when introducing multicomponent in this colloid preparation process, because the multicomponent element ion electric charge attribute added exists objective difference, make the preparation of the formation of colloid and three ordered big holes become very difficult.
Summary of the invention
The object of the present invention is to provide the three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2composite oxides are ZnO and Cu that a kind of duct is continuous in order, Lacking oxygen is adjustable 2the two component doping ZnO-Cu of O 2o-TiO 2composite oxides.
Present invention also offers the three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2the preparation method of composite oxides, by controlling copper source, the amount ratio in zinc source and titanium source, reaction time and temperature, realizing the modulation of Lacking oxygen, preparing ZnO-Cu 2o-TiO 2composite oxides.
Present invention also offers the three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2the application of composite oxides, the application in photocatalytic degradation.
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen provided by the invention is adjustable 2o-TiO 2composite oxides are ZnO and Cu 2the composite oxides of the two component doping of O, three-dimensional ordered macroporous structure, duct is orderly continuously, and macropore diameter is 150nm.
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen provided by the invention is adjustable 2o-TiO 2the preparation method of composite oxides, comprises the following steps:
A, at 25 DEG C, be solvent with ethylene glycol, add copper source and zinc source, after stirring and dissolving, add titanium source, sealing, stir, obtain mixed solution;
B, by after step a gained mixed solution heat ageing, immerse polystyrene colloid crystal template, obtain mixture, dry, roasting, obtains the three-dimensional ordered macroporous ZnO-Cu that Lacking oxygen is adjustable 2o-TiO 2composite oxides.
In step a, described copper source is Cu (NO 3) 23H 2o, described zinc source is Zn (NO 3) 26H 2o, described titanium source is butyl titanate.
Cu (NO in step a 3) 23H 2o, Zn (NO 3) 26H 2o molar concentration in ethylene glycol is respectively 0.010 ~ 0.029mol/L and 0.010 ~ 0.029mol/L, and the volume adding butyl titanate is the 25-40% of ethylene glycol volume.
After adding butyl titanate in step a, sealing, stirs 3-5h.
Heat ageing described in step b, specifically: at 30-50 DEG C of aging 3-5h.
In step b, immerse polystyrene colloid crystal template 12-24h at 25 DEG C after, obtain mixture.
In step b, solution with the amount ratio of Colloidal crystals is: every 3mL mixed solution adds 0.39g Colloidal crystals template.
The preparation method of the crystal template of polystyrene colloid described in step b is: the polystyrene microsphere being about 150nm by emulsion polymerization synthesis particle diameter.Specific as follows: to get 6mL styrene and be added to separatory funnel, the NaOH washing with 5% is until liquid is without pink, then to be washed till Ph with distilled water be 7; Pour washed styrene into there-necked flask, add 54ml water, logical nitrogen, and be placed on digital display thermostat water bath 70 DEG C heating, react 12 hours; The white emulsion of generation is poured into centrifuge tube centrifugal 12 hours after having reacted, then by this microballoon in centrifuges with the centrifugal 12h of the rotating speed of 2500rpm, drying at room temperature 12-24h subsequently, just can obtain polystyrene colloid crystal template.
In step b, described drying, condition is carry out 12-24h drying at 50-70 DEG C.
In step b, described roasting, condition is 500-600 DEG C of roasting temperature 3-5h.
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen provided by the invention is adjustable 2o-TiO 2the application of composite oxides, the application in photocatalytic degradation, the application especially in photocatalytic degradation of methylene blue.
First, ethylene glycol is introduced as solvent, reduces the exposure rate of titanium source in butyl titanate and copper ion and zinc ion, effectively can control the synthesis speed of this colloid, therefore it is carried out to the regulation and control of plastic speed without the need to introducing soda acid adjusting control agent.Secondly, for the TiO that two component adulterates 2, there is copper ion and zinc ion takes oxygen situation jointly by force, when the ratio of the copper nitrate introduced and zinc nitrate changes, as the Cu oxide oxygen content just respective change with variable valence.In the process, along with Cu 2+/ Zn 2+the change of concentration ratio, the concentration also respective change of Lacking oxygen, result is as the O of O1XPS in Fig. 3 D adscontent and O lattshown in the ratio of content.In addition, along with Cu 2+/ Zn 2+the change of concentration ratio, with the closely-related bandwidth of semiconductor, remarkable impact also occurs, result as shown in Figure 4 B.
Compared with prior art, the present invention as solvent, effectively can control the synthesis speed of this colloid by ethylene glycol, without the need to adding any soda acid adjusting control agent, just can realize the regulation and control of plastic speed and three-dimensional ordered macroporous ZnO-Cu 2o-TiO 2the preparation of composite oxides.Meanwhile, there is variable valence according to copper ion, and form copper ion and zinc ion takes oxygen situation jointly by force, therefore take the adjustment of the thing mass ratio of copper nitrate, zinc nitrate, just can realize ZnO-Cu easily 2o-TiO 2the modulation of oxygen vacancy concentration in composite oxides, thus improve its photocatalysis performance.
Accompanying drawing explanation
Figure 1A is ZnO-Cu prepared by embodiment 1 2o-TiO 2the SEM figure of composite oxides;
Figure 1B is ZnO-Cu prepared by embodiment 2 2o-TiO 2the SEM figure of composite oxides;
Fig. 1 C is ZnO-Cu prepared by embodiment 3 2o-TiO 2the SEM figure of composite oxides;
Fig. 2 is ZnO-Cu prepared by embodiment 1,2 and 3 2o-TiO 2the XRD figure of composite oxides; A is the XRD figure of embodiment 1; B is the XRD figure of embodiment 2; C is the XRD figure of embodiment 3;
Fig. 3 A is ZnO-Cu prepared by embodiment 1,2 and 3 2o-TiO 2the Zn2pXPS figure of composite oxides; Wherein: a is sample prepared by embodiment 1; B is sample prepared by embodiment 2; C is sample prepared by embodiment 3;
Fig. 3 B is ZnO-Cu prepared by embodiment 1,2 and 3 2o-TiO 2the Cu2p figure of composite oxides; Wherein: a is sample prepared by embodiment 1; B is sample prepared by embodiment 2; C is sample prepared by embodiment 3;
Fig. 3 C is ZnO-Cu prepared by embodiment 1,2 and 3 2o-TiO 2the XPS figure of the Ti2P of composite oxides; Wherein: a is sample prepared by embodiment 1; B is sample prepared by embodiment 2; C is sample prepared by embodiment 3;
Fig. 3 D is ZnO-Cu prepared by embodiment 1,2 and 3 2o-TiO 2the XPS figure of the O1s of composite oxides; Wherein: a is sample prepared by embodiment 1; B is sample prepared by embodiment 2; C is sample prepared by embodiment 3;
Fig. 4 A is ZnO-Cu prepared by embodiment 1,2 and 3 2o-TiO 2the UV-vis DRS absorption spectrum of composite oxides is wherein: a is sample prepared by embodiment 1; B is sample prepared by embodiment 2; C is sample prepared by embodiment 3;
Fig. 4 B is ZnO-Cu prepared by embodiment 1,2 and 3 2o-TiO 2the bandwidth figure of composite oxides; Wherein: a is sample prepared by embodiment 1; B is sample prepared by embodiment 2; C is sample prepared by embodiment 3;
Fig. 5 is ZnO-Cu prepared by embodiment 1,2 and 3 2o-TiO 2the Photocatalytic Degradation Property figure of composite oxides; A is the Photocatalytic Degradation Property figure of embodiment 1; B is the Photocatalytic Degradation Property figure of embodiment 2; C is the Photocatalytic Degradation Property figure of embodiment 3; D is unadulterated TiO 2(preparation method and embodiment 1,2,3 is similar) Photocatalytic Degradation Property figure.
Detailed description of the invention
Below by embodiment, the invention will be further described.
Embodiment 1
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2composite oxides, Cu (NO in middle preparation process 3) 23H 2o and Zn (NO 3) 26H 2o molar concentration in ethylene glycol is respectively 0.010mol/L, 0.029mol/L.
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2the preparation method of composite oxides, comprises the following steps:
A, at 25 DEG C, in the ethylene glycol of 20mL, add 0.207mmolCu (NO 3) 23H 2o and 0.571mmolZn (NO 3) 26H 2o magnetic agitation is dissolved, and adds 6.8mL butyl titanate subsequently and continues to stir 5h with preservative film sealing;
B, then gained solution is moved into 40 DEG C water-bath in carry out aging 3h, polystyrene colloid crystal template immerses in this solution subsequently, after 24h, carries out 12h drying to this mixture at 70 DEG C; Then to it at 600 DEG C of roasting temperature 3h, three-dimensional ordered macroporous ZnO-Cu 2o-TiO 2composite oxides.
The SEM of synthesized compound characterizes as shown in Figure 1A; Known by a in a, Fig. 3 BXPS figure in the XRD crystal formation in Fig. 2 shown in a and Fig. 3 AXPS figure, synthesized product is ZnO-Cu 2o-TiO 2composite oxides; From the XPS analysis of O1s shown in a in Fig. 3 DXPS figure, synthesized product has lower adsorb oxygen content (O ads/ O latt=0.15), corresponding lower oxygen vacancy concentration.
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2the application of composite oxides, the application in photocatalytic degradation;
Embody rule method is:
Take the ZnO-Cu prepared by embodiment 1 2o-TiO 2composite oxides 50mg is placed in quartz ampoule, add 10mg/L methylene blue solution 100mL subsequently, quartz ampoule is moved in darkroom and place 1 hour, be then put in the light-catalyzed reaction instrument of 500W xenon source, photocatalytic degradation is carried out to methylene blue, within every 1 hour, analyzes a catalytic performance.
In Fig. 5, a is catalytic performance result, by the visible synthesized ZnO-Cu of a in Fig. 5 2o-TiO 2composite oxides achieved the photocatalytic degradation efficiency to methylene blue 69% in 5 hours.
Embodiment 2
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2composite oxides, wherein Cu (NO in preparation process 3) 23H 2o and Zn (NO 3) 26H 2o molar concentration in ethylene glycol is respectively 0.019mol/L, 0.018mol/L.
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2the preparation method of composite oxides, comprises the following steps:
A, 25 DEG C in the ethylene glycol of 20mL, add 0.373mmolCu (NO 3) 23H 2o and 0.369mmolZn (NO 3) 26H 2o magnetic agitation is dissolved, and adds 6.8mL butyl titanate subsequently and continues to stir 5h with preservative film sealing;
B, then gained solution is moved into 30 DEG C water-bath in carry out aging 5h.Colloidal crystals template immerses in this solution subsequently, after 24h, carries out 20h drying to this mixture at 60 DEG C.Then to it at 550 DEG C of roasting temperature 5h, three-dimensional ordered macroporous ZnO-Cu 2o-TiO 2composite oxides.
The SEM of synthesized compound characterizes as shown in Figure 1B; Known by b in b, Fig. 3 BXPS figure in the XRD crystal formation in Fig. 2 shown in b and Fig. 3 AXPS figure, synthesized product is ZnO-Cu 2o-TiO 2composite oxides; From the XPS analysis of O1s shown in b in Fig. 3 DXPS figure, synthesized product has lower adsorb oxygen content (O ads/ O latt=0.19), corresponding relatively high oxygen vacancy concentration.
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2the application of composite oxides, the application in photocatalytic degradation.
Embody rule method is:
Take prepared ZnO-Cu 2o-TiO 2composite oxides 50mg is placed in quartz ampoule, add 10mg/L methylene blue solution 100mL subsequently, quartz ampoule is moved in darkroom and place 1 hour, be then put in the light-catalyzed reaction instrument of 500W xenon source, photocatalytic degradation is carried out to methylene blue, within every 1 hour, analyzes a catalytic performance.
In Fig. 5, b is catalytic performance result, by the visible synthesized ZnO-Cu of b in Fig. 5 2o-TiO 2composite oxides achieved the photocatalytic degradation efficiency to methylene blue 97% in 5 hours.
Embodiment 3
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2composite oxides, wherein Cu (NO in preparation process 3) 23H 2o and Zn (NO 3) 26H 2o molar concentration in ethylene glycol is respectively 0.029mol/L, 0.010mol/L.
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2the preparation method of composite oxides, comprises the following steps:
A, 25 DEG C in the ethylene glycol of 20mL, add 0.573mmolCu (NO 3) 23H 2o and 0.204mmolZn (NO 3) 26H 2o magnetic agitation is dissolved, and adds 6.8mL butyl titanate subsequently and continues to stir 5h with preservative film sealing;
B, then gained solution is moved into 50 DEG C water-bath in carry out aging 3h.Colloidal crystals template immerses in this solution subsequently, after 24h, carries out 24h drying to this mixture at 50 DEG C.Then to it at 500 DEG C of roasting temperature 3h, three-dimensional ordered macroporous ZnO-Cu 2o-TiO 2composite oxides.
The SEM of synthesized compound characterizes as shown in Figure 1 C; Known by c in c, Fig. 3 BXPS figure in the XRD crystal formation in Fig. 2 shown in c and Fig. 3 AXPS figure, synthesized product is ZnO-Cu 2o-TiO 2composite oxides; From the XPS analysis of O1s shown in c in Fig. 3 DXPS figure, synthesized product has lower adsorb oxygen content (O ads/ O latt=0.27), corresponding relatively high oxygen vacancy concentration.
The three-dimensional ordered macroporous ZnO-Cu that a kind of Lacking oxygen is adjustable 2o-TiO 2the application of composite oxides, the application in photocatalytic degradation.
Embody rule method is:
Take the ZnO-Cu prepared by embodiment 3 2o-TiO 2composite oxides 50mg is placed in quartz ampoule, add 10mg/L methylene blue solution 100mL subsequently, quartz ampoule is moved in darkroom and place 1 hour, be then put in the light-catalyzed reaction instrument of 500W xenon source, photocatalytic degradation is carried out to methylene blue, within every 1 hour, analyzes a catalytic performance.
In Fig. 5, c is catalytic performance result, by the visible synthesized ZnO-Cu of c in Fig. 5 2o-TiO 2composite oxides achieved the photocatalytic degradation efficiency to methylene blue 100% in 5 hours.
In comparison diagram 5, in a ~ c and Fig. 5, d is visible, doping ZnO-Cu 2o-TiO 2relative to unadulterated TiO 2, present better catalytic performance.

Claims (10)

1. the three-dimensional ordered macroporous ZnO-Cu that a Lacking oxygen is adjustable 2o-TiO 2composite oxides, is characterized in that, the three-dimensional ordered macroporous ZnO-Cu that described Lacking oxygen is adjustable 2o-TiO 2composite oxides are ZnO and Cu 2the composite oxides of the two component doping of O, three-dimensional ordered macroporous structure, duct is orderly continuously, and macropore diameter is 150nm.
2. the three-dimensional ordered macroporous ZnO-Cu that a Lacking oxygen according to claim 1 is adjustable 2o-TiO 2the preparation method of composite oxides, is characterized in that, described preparation method comprises the following steps:
A, at 25 DEG C, be solvent with ethylene glycol, add copper source and zinc source, after stirring and dissolving, add titanium source, sealing, stir, obtain mixed solution;
B, by after step a gained mixed solution heat ageing, immerse polystyrene colloid crystal template, obtain mixture, dry, roasting, obtains the three-dimensional ordered macroporous ZnO-Cu that Lacking oxygen is adjustable 2o-TiO 2composite oxides.
3. preparation method according to claim 2, is characterized in that, in step a, described copper source is Cu (NO 3) 23H 2o, described zinc source is Zn (NO 3) 26H 2o, described titanium source is butyl titanate.
4. preparation method according to claim 2, is characterized in that, Cu (NO in step a 3) 23H 2o, Zn (NO 3) 26H 2o molar concentration in ethylene glycol is respectively 0.010 ~ 0.029mol/L and 0.010 ~ 0.029mol/L, and the volume adding butyl titanate is the 25-40% of ethylene glycol volume.
5. preparation method according to claim 2, is characterized in that, after adding butyl titanate in step a, sealing, stirs 3-5h.
6. preparation method according to claim 2, is characterized in that, heat ageing described in step b, specifically: 30-50 DEG C of aging 3-5h.
7. preparation method according to claim 2, is characterized in that, in step b, immerses polystyrene colloid crystal template 12-24h.
8. preparation method according to claim 2, is characterized in that, in step b, described roasting, condition is 500-600 DEG C of roasting temperature 3-5h.
9. the three-dimensional ordered macroporous ZnO-Cu that the Lacking oxygen prepared by an any one of claim 2-8 is adjustable 2o-TiO 2the application of composite oxides, is characterized in that, the application in photocatalytic degradation.
10. application according to claim 8, is characterized in that, the application in photocatalytic degradation of methylene blue.
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CN110102248A (en) * 2019-06-21 2019-08-09 清华大学 A kind of surface oxygen defect porous metal oxide material and its preparation and application
CN113540390A (en) * 2021-06-29 2021-10-22 哈尔滨工业大学 Preparation method and application of dynamic interface coating of metal zinc cathode of zinc ion battery
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