CN103638958B - ZnS-CaTaO2N compound photocatalyst and preparation method thereof - Google Patents
ZnS-CaTaO2N compound photocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN103638958B CN103638958B CN201310644499.5A CN201310644499A CN103638958B CN 103638958 B CN103638958 B CN 103638958B CN 201310644499 A CN201310644499 A CN 201310644499A CN 103638958 B CN103638958 B CN 103638958B
- Authority
- CN
- China
- Prior art keywords
- zns
- catao
- mixed solution
- solution
- catao2n
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a ZnS-CaTaO2N compound photocatalyst and a preparation method thereof, and belongs to the field of inorganic functional materials. The key point of the technical scheme provided by the invention is that the ZnS-CaTaO2N compound photocatalyst is formed from ZnS and CaTaO2N powder bodies through compounding, and the molar ratio of the ZnS to CaTaO2N is (5-15): 1. The invention also discloses the preparation method of the ZnS-CaTaO2N compound photocatalyst. Compared with the prior art, the ZnS-CaTaO2N compound photocatalyst and the preparation method provided by the invention have the advantages that the compounding of the ZnS and the CaTaO2N can greatly expand the spectral response range of the ZnS, the ZnS in a visible light region is well absorbed, the ZnS solar use ratio is improved, the compounding of the ZnS and the CaTaO2N can effectively reduce the compounding probability of photoproduction electrons and holes, and the photocatalytic activity of the ZnS is improved.
Description
Technical field
The invention belongs to inorganic environment-friendly catalysis material technical field, be specifically related to a kind of ZnS-CaTaO
2n composite photo-catalyst and preparation method thereof.
Background technology
The advantages such as efficiency is high, energy consumption is low, reaction condition is gentle, applied widely and secondary pollution is few that utilize Nano semiconductor photocatalysis degradation organic contaminant to have, cause the attention of increasing researcher.Due to nontoxic, cost is low and have unique physics and chemical property, is that the photocatalytic-oxidation formed material of representative is a kind of new material for photocatalysis treatment sewage with ZnS.ZnS is a kind of II-VI group compound direct-bandgap semi-conducting material, and energy gap is 3.6 eV, just can excite its catalytic activity be only less than the ultraviolet of 344 nm at wavelength under.In the solar energy arriving ground, the energy of this wave band is still less than 5%, and the ratio of visible light part accounts for about 45% of solar energy.In addition, ZnS photochemical catalyst is the easy compound of light induced electron and hole in photocatalytic process, and catalytic efficiency is low.Therefore, how to widen ZnS photochemical catalyst spectral response range, improve the Focal point and difficult point that its photo-quantum efficiency becomes photocatalysis disciplinary study.
CaTaO
2n is a kind of transition metal oxynitrides, and because divalence oxygen element part is replaced by the trivalent nitrogen element that electronegativity is less, metal cation is more or less reduced, and crystal structure changes, CaTaO
2thus N shows optical, electrical, the magnetic that make new advances, mechanical property.Research shows, CaTaO
2the energy gap of N is 2.4 eV, and energy absorbing wavelength is less than the visible ray of 517 nm.In order to widen the spectral response range of ZnS, by itself and the CaTaO with ideal bandgap
2n phase compound, utilizes the energy level difference between two kinds of semiconductors that photogenerated carriers can be made to be injected on the energy level of another kind of semiconductor by a kind of energy level of semiconductive particles, electric charge is effectively separated, and is the effective way improving ZnS solar energy utilization ratio and photo-quantum efficiency.The conduction band potential E of ZnS photochemical catalyst
cB=-1.04 eV, valence band electromotive force E
vB=2.56 eV, and CaTaO
2the conduction band potential E of N photochemical catalyst
cB=-1.26 eV, valence band electromotive force E
vB=1.34 eV.At ZnS/CaTaO
2in N composite semiconductor, CaTaO
2the conduction band potential of N is more negative, and light induced electron is easily from the CaTaO that energy level is low
2n conduction band moves on the high ZnS conduction band of energy level; Meanwhile, the valence band electromotive force corrigendum of ZnS, photohole easily moves to the low CaTaO of energy level from the ZnS valence band that energy level is high
2in N valence band, thus improve the separation rate of photogenerated charge, extend the spectral response range of ZnS.
Summary of the invention
It is high that the technical problem that the present invention solves there is provided a kind of solar energy utilization ratio, the ZnS-CaTaO that photocatalytic activity is good
2n composite photo-catalyst.
The present invention solve another technical problem there is provided a kind of simple to operate and be easy to realize ZnS-CaTaO
2the preparation method of N composite photo-catalyst.
Technical scheme of the present invention is: a kind of ZnS-CaTaO
2n composite photo-catalyst, it is characterized in that by ZnS and CaTaO
2n powder compound and the ZnS-CaTaO formed
2n composite photo-catalyst, wherein ZnS and CaTaO
2the mol ratio of N is 5-15:1.
ZnS-CaTaO of the present invention
2the preparation method of N composite photo-catalyst, it is characterized in that comprising the following steps: the ratio absolute methanol of tantalic chloride, calcium carbonate and citric acid 1:1:10 is in molar ratio made into mixed solution A by (1), under the condition stirred, in mixed solution A, add ethylene glycol form mixed solution B, wherein the addition of ethylene glycol is 5 times of citric acid mole in mixed solution A, then mixed solution B is kept in the water-bath of 30 DEG C 2 hours obtaining wet gel, wet gel is through 120 DEG C of dry xerogel; (2) by the xerogel of step (1) gained in air atmosphere 500 DEG C calcining 2 hours, then under ammonia atmosphere 950 DEG C calcining 20 hours CaTaO
2n powder; (3) zinc nitrate solution is prepared, by step (2) gained CaTaO under the condition stirred
2n powder joins in zinc nitrate solution and obtains mixed solution C, wherein zinc nitrate and the CaTaO added
2the mol ratio of N powder is 5-15:1; (4) preparing thiourea solution, under the condition stirred, is that thiourea solution to be added drop-wise in mixed solution C and to form mixed solution D by the ratio of 1:1 according to the mol ratio of thiocarbamide and zinc nitrate; (5) mixed solution D is transferred in hydrothermal reaction kettle, after keeping after 6-24 hour through 150-180 DEG C, obtain the ZnS-CaTaO with high catalytic activity
2n composite photo-catalyst.
ZnS-CaTaO of the present invention
2the preparation method of N composite photo-catalyst, is characterized in that: in described step (3), the molar concentration of zinc nitrate solution is 0.1-0.5mol/L.ZnS-CaTaO of the present invention
2the preparation method of N composite photo-catalyst, is characterized in that: in described step (4), the molar concentration of thiourea solution is 0.1-0.5mol/L.
The present invention compared with prior art has following remarkable advantage: 1, ZnS and CaTaO
2the compound of N can widen the spectral response range of ZnS greatly, makes ZnS have good absorption in visible region, improves the utilization rate of solar energy; 2, ZnS and CaTaO
2the compound of N can effectively reduce the probability of recombination in light induced electron and hole, improves the photocatalytic activity of ZnS; 3, ZnS-CaTaO of the present invention
2the preparation method of N composite photo-catalyst is simple, is easy to control.
Accompanying drawing explanation
Fig. 1 is under the high voltage mercury lamp radiation of 300 W, the ZnS-CaTaO prepared by the embodiment of the present invention 1
2n composite photo-catalyst and commercial ZnS (P25) are to the correlation curve (operating condition: catalytic amount: 0.5 g/L of methylene blue degraded situation; The concentration of methylene blue: 50 mg/L).
Detailed description of the invention
Be described in further details foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
(1) amount of substance is respectively the tantalic chloride of 0.001mol, 0.001mol, 0.01mol, calcium carbonate and citric acid to join 10mL absolute methanol and be made into mixed solution A, under the condition stirred, in mixed solution A, add 0.05mol ethylene glycol obtain mixed solution B, then mixed solution B is kept in the water-bath of 30 DEG C 2 hours obtaining wet gel, wet gel is through 120 DEG C of dry xerogel;
(2) xerogel of step (1) gained is calcined 2 hours through 500 DEG C in air atmosphere, then under ammonia atmosphere, within 20 hours, obtain CaTaO through 950 DEG C of calcinings
2n powder;
(3) preparing 50mL molar concentration is the zinc nitrate solution of 0.1mol/L, by the CaTaO of step (2) gained 0.001mol under the condition stirred
2n powder joins in zinc nitrate solution and obtains mixed solution C;
(4) preparing 50mL molar concentration is the thiourea solution of 0.1mol/L, under agitation, is added drop-wise to by thiourea solution in mixed solution C and forms mixed solution D;
(5) mixed solution D is transferred in hydrothermal reaction kettle, after keeping 24 hours through 150 DEG C, obtain the ZnS-CaTaO with high catalytic activity
2n composite photo-catalyst.The ZnS-CaTaO prepared as seen from Figure 1
2n composite photo-catalyst has higher degradation rate compared with ZnS photochemical catalyst under identical degradation time, therefore ZnS-CaTaO
2n composite photo-catalyst not only increases photocatalytic activity, has good photocatalysis effect, also improves the utilization ratio to solar energy simultaneously.
Embodiment 2
(1) amount of substance is respectively the tantalic chloride of 0.001mol, 0.001mol, 0.01mol, calcium carbonate and citric acid to join 10mL absolute methanol and be made into mixed solution A, under the condition stirred, in mixed solution A, add 0.05mol ethylene glycol obtain mixed solution B, then mixed solution B is kept in the water-bath of 30 DEG C 2 hours obtaining wet gel, wet gel is through 120 DEG C of dry xerogel;
(2) xerogel of step (1) gained is calcined 2 hours through 500 DEG C in air atmosphere, then under ammonia atmosphere, within 20 hours, obtain CaTaO through 950 DEG C of calcinings
2n powder;
(3) preparing 50mL molar concentration is the zinc nitrate solution of 0.2mol/L, by the CaTaO of step (2) gained 0.001mol under the condition stirred
2n powder joins in zinc nitrate solution and obtains mixed solution C;
(4) preparing 50mL molar concentration is the thiourea solution of 0.2mol/L, under agitation, is added drop-wise to by thiourea solution in mixed solution C and forms mixed solution D;
(5) mixed solution D is transferred in hydrothermal reaction kettle, after keeping after 12 hour through 160 DEG C, obtain the ZnS-CaTaO with high catalytic activity
2n composite photo-catalyst.
Embodiment 3
(1) amount of substance is respectively the tantalic chloride of 0.001mol, 0.001mol, 0.01mol, calcium carbonate and citric acid to join 10mL absolute methanol and be made into mixed solution A, under the condition stirred, in mixed solution A, add 0.05mol ethylene glycol obtain mixed solution B, then mixed solution B is kept in the water-bath of 30 DEG C 2 hours obtaining wet gel, wet gel is through 120 DEG C of dry xerogel;
(2) xerogel of step (1) gained is calcined 2 hours through 500 DEG C in air atmosphere, then under ammonia atmosphere, within 20 hours, obtain CaTaO through 950 DEG C of calcinings
2n powder;
(3) preparing 30mL molar concentration is the zinc nitrate solution of 0.5mol/L, by the CaTaO of step (2) gained 0.001mol under the condition stirred
2n powder joins in zinc nitrate solution and obtains mixed solution C;
(4) preparing 30mL molar concentration is the thiourea solution of 0.5mol/L, under agitation, is added drop-wise to by thiourea solution in mixed solution C and forms mixed solution D;
(5) mixed solution D is transferred in hydrothermal reaction kettle, after keeping after 6 hour through 180 DEG C, obtain the ZnS-CaTaO with high catalytic activity
2n composite photo-catalyst.
Embodiment above describes general principle of the present invention, principal character and advantage.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; under the scope not departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.
Claims (3)
1. a ZnS-CaTaO
2the preparation method of N composite photo-catalyst, it is characterized in that concrete synthesis step is: the ratio absolute methanol of tantalic chloride, calcium carbonate and citric acid 1:1:10 is in molar ratio made into mixed solution A by (1), under the condition stirred, in mixed solution A, add ethylene glycol form mixed solution B, wherein the addition of ethylene glycol is 5 times of citric acid mole in mixed solution A, then mixed solution B is kept in the water-bath of 30 DEG C 2 hours obtaining wet gel, wet gel is through 120 DEG C of dry xerogel; (2) by the xerogel of step (1) gained in air atmosphere 500 DEG C calcining 2 hours, then under ammonia atmosphere 950 DEG C calcining 20 hours CaTaO
2n powder; (3) zinc nitrate solution is prepared, by step (2) gained CaTaO under the condition stirred
2n powder joins in zinc nitrate solution and obtains mixed solution C, wherein zinc nitrate and the CaTaO added
2the mol ratio of N powder is 5-15:1; (4) preparing thiourea solution, under the condition stirred, is that thiourea solution to be added drop-wise in mixed solution C and to form mixed solution D by the ratio of 1:1 according to the mol ratio of thiocarbamide and zinc nitrate; (5) mixed solution D is transferred in hydrothermal reaction kettle, after keeping after 6-24 hour through 150-180 DEG C, obtain the ZnS-CaTaO with high catalytic activity
2n composite photo-catalyst, wherein ZnS and CaTaO
2the mol ratio of N is 5-15:1.
2. ZnS-CaTaO according to claim 1
2the preparation method of N composite photo-catalyst, is characterized in that: in step (3), the molar concentration of zinc nitrate solution is 0.1-0.5mol/L.
3. ZnS-CaTaO according to claim 1
2the preparation method of N composite photo-catalyst, is characterized in that: in step (4), the molar concentration of thiourea solution is 0.1-0.5mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310644499.5A CN103638958B (en) | 2013-12-05 | 2013-12-05 | ZnS-CaTaO2N compound photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310644499.5A CN103638958B (en) | 2013-12-05 | 2013-12-05 | ZnS-CaTaO2N compound photocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103638958A CN103638958A (en) | 2014-03-19 |
| CN103638958B true CN103638958B (en) | 2015-06-03 |
Family
ID=50244325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310644499.5A Expired - Fee Related CN103638958B (en) | 2013-12-05 | 2013-12-05 | ZnS-CaTaO2N compound photocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103638958B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4107792B2 (en) * | 2000-08-28 | 2008-06-25 | 独立行政法人科学技術振興機構 | Photocatalyst composed of metal oxynitride having visible light response |
| CN101204652A (en) * | 2007-12-19 | 2008-06-25 | 中国科学院上海硅酸盐研究所 | High efficiency semiconductor photocatalysis and preparation method thereof |
| CN102000591B (en) * | 2010-11-03 | 2012-07-25 | 哈尔滨工业大学 | Composite photocatalyst and preparation method thereof |
-
2013
- 2013-12-05 CN CN201310644499.5A patent/CN103638958B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103638958A (en) | 2014-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103007971B (en) | Zinc tungstate/bismuth oxyiodide heterojunction visible light photocatalysis material and fabrication method thereof | |
| CN102600857A (en) | Preparation method of carbon ball-loaded CuO-BiVO4 heterojunction compound photocatalyst | |
| CN104307538B (en) | Preparation and application methods of high-efficiency composite photocatalytic material | |
| CN104096558B (en) | A kind of bismuth molybdate-zinc oxide composite photocatalyst and preparation method thereof | |
| CN103301833B (en) | Yb<3+>-Tm<3+>-Li<+> triple-doped Bi2WO6/CNTs (carbon nanotubes) upconversion photocatalytic material | |
| CN105664995A (en) | Multi-element co-doped nano titanium dioxide photocatalytic material | |
| CN107098429B (en) | BiVO4/BiPO4Composite material and preparation method and application thereof | |
| Hojamberdiev et al. | Er3+-doping induced formation of orthorhombic/monoclinic Bi5O7I heterostructure with enhanced visible-light photocatalytic activity for removal of contaminants | |
| CN101791562B (en) | Method for preparing ferrum-fluorine-codoped nano-titanium dioxide visible light photocatalyst | |
| CN106732660A (en) | A kind of preparation method of Graphene small particle zinc sulphide/silver sulfide hetero-junctions visible light catalytic material | |
| CN105772051A (en) | Bi2O2CO3-BiFeO3 compound photocatalyst and preparing method thereof | |
| CN105562034A (en) | CdS/BiVO4 compound semiconductor photocatalyst and preparation and application thereof | |
| CN103611560B (en) | TiO2-CaTaO2N composite photocatalyst and preparation method thereof | |
| CN105854912A (en) | BiPO4-WO3 composite photocatalyst and preparation method thereof | |
| CN105772045A (en) | BiPO4-ZnFe2O4 compound catalyst and preparing method thereof | |
| CN104841457A (en) | Zinc sulfide-zinc oxide hetero-junction nano material and solid-phase preparation method thereof | |
| CN104028274A (en) | LaFeO3/TiO2 composite nanotube with visible light activity, and preparation method thereof | |
| CN105771953A (en) | Preparation method of zinc titanate and titanium dioxide composite nano material | |
| CN103785429A (en) | Silver phosphate/graphene/titanium dioxide nano composite and preparation method thereof | |
| CN104971753A (en) | Bi2O2CO3-BiPO4 composite photocatalyst and preparation method thereof | |
| CN104148093A (en) | Preparation method for Bi2WO6-MoS2 composite photocatalyst | |
| CN105797760A (en) | Bi2O2CO3-WO3 composite photocatalyst and preparation method thereof | |
| CN103611557B (en) | ZnO-SrTaO2N composite photocatalyst and preparation method thereof | |
| CN106345509B (en) | A solvothermal method is adopted to prepare C3N4/CaTi2O5Method for compounding materials | |
| CN103611559B (en) | Bi2WO6-SrTaO2N composite photocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150603 Termination date: 20151205 |
|
| EXPY | Termination of patent right or utility model |