CN1544144A - Visible light response photocatalyst and application thereof - Google Patents
Visible light response photocatalyst and application thereof Download PDFInfo
- Publication number
- CN1544144A CN1544144A CNA2003101062806A CN200310106280A CN1544144A CN 1544144 A CN1544144 A CN 1544144A CN A2003101062806 A CNA2003101062806 A CN A2003101062806A CN 200310106280 A CN200310106280 A CN 200310106280A CN 1544144 A CN1544144 A CN 1544144A
- Authority
- CN
- China
- Prior art keywords
- photocatalyst
- light
- visible
- catalyst
- visible light
- 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.)
- Granted
Links
Abstract
The invention provides high-activity photocatalysts absorbing UV rays and visible lights in the sunlight, as well as a method of decomposing harmful chemical matters and decomposing water to prepare hydrogen by these photocatalysts, which are compound oxide semiconductors formed of In and 5A element in periodic table of elements as well as transition metallic element M and expressed by the formula In1-xMxAO4 derived from displacing part of In in oxide semiconductor InAO4, where the sum of mole numbers of In and M is equal to mole number of A, and these compound oxide semiconductors acts as photocatalysts. It uses these photocatalysts to realize decomposition of harmful chemical matters and of water to prepare hydrogen under the irradiation with the sunlight containing UV rays and visible lights.
Description
The technical field is as follows:
the present invention relates to a photocatalyst responsive to ultraviolet light and visible light and use thereof, and more particularly to a highly active photocatalyst composed of an indium-based composite oxide semiconductor capable of efficiently absorbing ultraviolet light and visible light in sunlight, and use thereof for decomposing harmful chemical substances and producing hydrogen.
Second, technical background
At present, the living and life quality improvement of human beings are directly influenced by the deep environmental and energy problems caused by the restriction of fossil resources and the large consumption of fossil resources, such as global warming, environmental deterioration and the like, and the development of green and safe new energy is urgently needed by human beings. Although nuclear power generation has been put into practical use as a source of new energy, problems in terms of safety, waste disposal, and the like have arisen.
One of the ways to solve the problem is to use solar energy. During the year, the solar energy reaching the earth's surface is enormous, which corresponds to as much as 10,000 times the annual energy consumption of humans. One of the purposes of research on visible light semiconductor photocatalysts is to simulate photosynthesis of plants and develop artificial photosynthesis technology, so that hydrogen and oxygen as green fuels are directly produced by using inexhaustible sunlight and water. The decomposition reaction of water is an energy storage type reaction as shown in (1), and the reaction of photosynthesis is the same as the above reaction in consideration of the light-generating reaction conditions necessary for oxygen generation, and is also a decomposition reaction:
The photocatalyst, upon absorbing photons above its band gap energy, generates holes and electrons. These holes and electrons undergo oxidation and reduction reactions, respectively, to generate oxygen and hydrogen. In view of the utility of photocatalysts, it is indispensable to use sunlight as a light source. The intensity of visible light with a wavelength around 500nm in sunlight irradiated to the earth surface is the largest, and the energy of the visible light region with a wavelength of 400nm to 750nm is about 43% of the total energy of sunlight. On the other hand, the ultraviolet ray having a wavelength of 440nm or less is less than 5%. Therefore, in order to utilize the solar spectrum efficiently, it is desired to find a photocatalyst having catalytic activity under visible light.
However, although the conventional semiconductor photocatalyst can generate hydrogen and oxygen under irradiation of ultraviolet rays having high energy, examples of the production of hydrogen using a visible-light-responsive semiconductor photocatalyst are very limited, and the activity is also low. And the full utilization of visible light is the basic premise of high-efficiency utilization of sunlight.
In recent years, research on the decomposition of harmful chemicals using photocatalysts has attracted attention. Although applications of titanium dioxide for decomposing organic substances such as pesticides and malodorous substances in water and the atmosphere and for self-cleaning by coating on solid surfaces have been developed, titanium dioxide hardly utilizes visible light. The efficiency of the above applications can be greatly improved if there is a visible light photocatalyst available. The holes in the valence band in oxide semiconductors have a very strong oxidizing power and can oxidize water and most organic and other electron donors, thereby releasing oxygen. And the conduction band electrons have reducing ability and can reduce water to generate hydrogen. That is, the conduction band level is higher than the oxidation potential of oxygen, and the valence band level is lower than the reduction potential of hydrogen, which are indispensable conditions for achieving water decomposition. A photocatalyst capable of decomposing water to generate hydrogen and oxygen has strong oxidizing and reducing abilities, and thus is expected to be applied to the above-mentioned fields.
Third, the invention
The purpose of the invention is: a highly active photocatalyst comprising an indium-based composite oxide semiconductor which efficiently absorbs ultraviolet rays and visible light in sunlight, and a method for decomposing harmful chemical substances and producing hydrogen using the photocatalyst are provided.
The purpose of the invention is realized as follows:
1. the semiconductor photocatalyst is composed of a compound oxide semiconductor formed of indium, an element 5A (A: 5A element) In the periodic Table of the elements, and a transition metal element having a valence of 2, wherein the sum of the number of moles of In and M is equal to the number of moles of A.
2. Oxide semiconductor InAO composed of indium and 5A element in periodic table4An oxide semiconductor represented by (A: 5A element) and a chemical formula In which a part of indium is replaced by a transition metal M1-xMxAO4The composite oxide semiconductor having a wolfianite-type crystal structure is represented by the photocatalyst recorded in claim 1.
3. The above-mentioned photocatalyst recorded in 1-2 is an oxide semiconductor comprising at least one element selected from Nb, Ta and V, and M is at least one element selected from Cr, Mn, Fe, Co, Ni, Cu and Zn.
4. The oxide semiconductor responding to visible light is the photocatalyst recorded in 1 to 3 above.
5. Adopts the chemical formula In1-xNixTaO4Or In1-xNixNbO4The compound oxide semiconductor shown above was used as the photocatalyst for the above 1-4records.
6. A photocatalyst of the cocatalyst reported in 1-5 above.
7. A method of decomposing a harmful chemical substance by irradiating light containing ultraviolet rays and visible light with the photocatalyst of the above 1 to 6.
8. A method for producing hydrogen by irradiating a photocatalyst as described in 1 to 6 with a light beam containing ultraviolet rays and visible light.
9. A method for producing hydrogen by completely decomposing water into hydrogen and oxygen by irradiating the photocatalyst of 1 to 6 with light containing ultraviolet rays or visible light.
In the present invention, the photocatalyst used is represented by the expression In1-xMxAO4Wherein M is a metal element having a valence of 2 and is selected from Cr, Mn, Fe, Co, Ni, Cu, Zn and the like, A is a 5A element having a valence of 5 and is selected from V, Nb, Ta and the like, and oxygen in the chemical formula is 4 atoms, and the number of oxygen atoms is actually less than 4 due to the presence of defects such as oxygen vacancies. It is considered that if M having a valence of 2 becomes much larger, the amount of oxygen becomes less than 4. x is a number greater than 0 and less than 1. The basic formula is represented by the general formula B3+A5+O4Having a Wolfranite crystal structure, it suffices that x in the compound is in a range in which the crystal structure thereof is kept stable.
The compound oxide semiconductor of the present invention can be synthesized by a general solid-phase reaction method, in which oxides each having each metal component are mixed in a stoichiometric ratio and calcined under air at normal pressure. For easily sublimable raw materials, a little more is required in parts. In addition, various methods such as various sol-gel (sol-gel) methods and citric acid complexation methods using a metal alkoxide or a metal salt as a raw material can also be used.
In order to utilize light more efficiently, the photocatalyst in the present invention is desirably shaped into fine particles to obtain a large surface area.
The oxide produced by the solid phase reaction method has a large particle size and a small surface area, but the particle diameter can be reduced by a pulverizing means such as a ball mill. The particle size is generally about 10 μm to 200. mu.m, preferably 50 μm or less. The fine particles may be pressed into a plate shape for use. The method of solid phase reaction can be seen in the related inventions 92107282, 98111231 of the present applicant: xin quan, etc.
The surface of the semiconductor of the present invention may be modified with a commonly used promoter, such as noble metals including Pt and Pd, transition metals including Ni and Co, NiO, IrO2, NiOx、RuO2Etc. as a photocatalyst having a microstructure. The preparation method can be an impregnation method, an electrodeposition method or the like. The impregnation method is to impregnate the semiconductor oxide into the aqueous solution of the compound such as chloride, nitrate and the like of the active species of the oxide, then to dry at 100-200 ℃ for about 2-5 hours, and to calcine at 800 ℃ or lower (preferably 200-500 ℃) for 2-5 hours under the reducing gas and/or the oxidizing gas. The cocatalyst is used in an amount of 0.01 to 10 wt%, preferably 0.1 to 5 wt%.
The reaction solution used for carrying out the complete decomposition reaction of water is not limited to pure water. In general, the water decomposition reaction can also be caused to occur in brine, in which carbonate or bicarbonate, an iodide salt, and a bromide salt are usually dissolved.
Thephotocatalyst of the present invention is added to the aqueous solution. The amount of catalyst added should be substantially that amount which ensures that the incident light can be absorbed efficiently. The contrast area is 25cm2In the case of (3), the amount of the photocatalyst to be added is 0.05 to 10g, preferably 0.2 to 3 g. By irradiating the aqueous solution to which the catalyst for photodecomposition is added with light in this manner, water is decomposed to generate oxygen. For example, the photocatalyst of the present invention may be added to pure water, and water may be decomposed by irradiation with visible light to simultaneously generate oxygen and hydrogen in a stoichiometric ratio of 2: 1. The spectrum of the light used to irradiate the water must contain wavelengths that can be absorbed by the semiconductor. Sunlight can also be irradiated in the present invention.
The specific reaction method may be a gas phase reaction in which the catalyst is suspended in an aqueous solution containing organic substances and irradiated with light, or a gas phase reaction in which the catalyst is fixed to a base and the liquid flows slowly over the surface of the base and the malodorous substance is decomposed in a gasification bed.
The photocatalyst of the invention can be used for not only the complete decomposition of water, but also a plurality of photocatalytic reactions. For example, when complex organic molecules are decomposed, molecules of pollutants such as alcohol, agricultural chemicals, dyes, intermediates, and offensive odors generally function as electron donors, and these molecules are oxidized by holes and decomposed, and at the same time, are reduced by electrons to generate hydrogen, or oxygen is reduced by electrons. The specific reaction apparatus may be one in which the catalyst is suspended in an aqueous solution containing organic substances and irradiated with light, one in which the catalyst is fixed toa base, or one in which the catalyst is subjected to a gas phase reaction in decomposing malodorous substances.
The effects of the invention also include: as for the photocatalyst for completely decomposing water by directly using solar energy, the currently used photocatalyst is active only under ultraviolet rays, and cannot effectively use visible light, which accounts for the most part of solar energy. By means of the invention, water can be decomposed into hydrogen and oxygen by means of visible light. In the future, the artificial pool can be filled with the photocatalyst, and the hydrogen is efficiently and massively produced by endless solar energy, which provides a promising approach for solving the energy problem.
Fourth, detailed description of the invention
Example 1
In the chemical formula of the invention1-xMxAO4In (c), In is synthesized using indium, elements M and A1-xMxAO4. Oxides of various components were synthesized by a solid phase method according to the stoichiometric ratio. The catalyst is prepared by adjusting (1-x) mol In by using a stoichiometric ratio2o3x is (0-1), x mol NiO (x is 0-1) and 1mol Ta2O5(Table 1). For example, when x is 0.2, In0.8Ni0.2TaO4Respectively weigh In2O83.201g、NiO 0.431g、Ta2O56.368 g. Placing the raw materials inPlacing into an alumina crucible, pre-sintering at 900 deg.C for 24 hr in an electric furnace under normal pressure in air, and repeating the calcination at 1200 deg.C for 50 hr for 3 times. After calcination, the calcined material is ground into a powder having a size of 10 μm or less in a mortar. XRD and SEM-EDS were used to studythe chemical composition and crystal structure of the catalyst before and after the photoreaction. Through Rietveld analysis, the oxide has a monoclinic crystal structure, space group is P2/C, and the crystal configuration is a layered Wolframate structure. The electrons of the semiconductor having the Wolframite type crystal structure are relatively easily moved. The energy gap of the material is below 2.5Ev by ultraviolet absorption spectrum measurement, so that the material has visible light responsiveness.
The oxide semiconductor is doped with 1.0 wt% of NiOx promoter by Ni (NO)3)2Immersing in an aqueous solution, drying at 200 ℃ for 5 hours, reducing with hydrogen at 500 ℃ and oxidizing at 200 ℃.
0.5g of NiOx/In1-xNixTaO4Suspended in 250ml of pure water to cause photodecomposition reaction of water. A closed-loop catalytic reaction apparatus was used, and visible light was externally irradiated while magnetic stirring was performed. A300W xenon lamp was used as a light source, and a vessel made of borosilicate glass was used as a reaction vessel. Light of a long wavelength is obtained by passing the light through a chopper filter (wavelength>420nm), and then the photocatalyst is irradiated with the light. The detection and quantification of the generated hydrogen and oxygen was performed by gas chromatography.
The experimental results show that: the stoichiometric ratio of hydrogen and oxygen was 2: 1, thus demonstrating: complete decomposition of water is achieved by means of visible light. The hydrogen and the rate of generation thereof are shown in table 1. This is greatly different from the performance when a part of In is replaced with Ni. In such semiconductors, the activity is maximal when x is 0.1.
In1-xMxAO4In the same way as the above embodiments, IrO is used2、CoO、NiOx、RuO2Oxides such as CuO, ZnO and the like can replace NiO, and similar composite oxides can be obtained, and the effect is also similar.
In the same way, V2O5、Nb2O5Substituted Ta2O5Similar to the above embodiment, similar composite oxides can be obtained, and the effects are also similar.
Example 2
By RuO2Instead of NiOx as promoter in example 1. In1-xNixTaO4Semiconductor incorporation of 1.0 wt% RuO2By RuCl4Impregnation with an aqueous solution, drying at 200 ℃ for 5 hours, and calcining at 500 ℃ for 2 hours under an oxidizing gas. The results are shown in Table 1. At this time, it can also be known that: the water is completely decomposed under visible light. Embodiments of IrO2 are as above.
The Pt noble metal and the Co transition metal are deposited In by an electrodeposition method, namely an electrolysis process1-xNixTaO4On the semiconductor, a photocatalyst having a microstructure was obtained. The results are similar to those in Table 1. Pt carbon can also be used for aggregationIn1-xNixTaO4And the like.
Example 3
In order to confirm that the decomposition of organic substances proceeds relatively efficiently under visible light, the decomposition of methanol was carried out in an aqueous solution. Pt (0.1 wt%) was used as In0.9Ni0.1TaO4The cocatalyst of (1). 0.5g of the photocatalyst was suspended in a mixture of 240ml of pure water and 10ml of methanol to cause photodecomposition reaction. A closed-loop catalytic reaction apparatus was used, and visible light was externally irradiated while magnetic stirring was performed. A300W xenon lamp was used as a light source, and a vessel made of borosilicate glass was used as a reaction vessel. Light from a light source is passed through a chopper filter (wavelength>420nm) to obtain light of a long wavelength, and then irradiated to a sample (photocatalyst). The detection and quantification of the hydrogen and oxygen produced was performed by gas chromatography. The experimental results show that hydrogen is stably produced at a rate of 146. mu. mol/h, and oxygen is not produced. This indicates that under visible light irradiation, the following reaction occurs: the holes oxidatively decompose methanol and the electrons reduce water to produce hydrogen.
Decomposition of organic pollutants: for removing complex chemical substances such as phenol, acid, ketone, aldehyde and the like in the wastewater, the method for treating the wastewater by using titanium dioxide can be seen as the following method: southeast university CN01238388 "administers the photocatalytic reactor of waste water waste gas.
In this example, the treatment of phenol-containing wastewater (wastewater from terephthalic acid production) was carried out under the above conditions, in which 0.5g of the photocatalyst was placed in 250ml of wastewater, and the COD removal rate was 80% or more by direct irradiation with a xenon lamp for 2 hours.
This example was used for the treatment of gulonic acid wastewater: 0.5g of photocatalyst is placed into a 250ml wastewater xenon lamp to directly irradiate for 2 hours, and the decoloring effect is obvious by visual observation.
Example 4
In example 3, Pt (1 wt%) was used as In0.8Cu0.2TaO4Pt (1 wt%) as In0.8Fe0.2TaO4The cocatalyst of (1). 0.5g of the photocatalyst was suspended in a mixture of 240ml of pure waterand 10ml of methanol to cause photodecomposition of water. A closed-loop catalytic reaction apparatus was used, and visible light was externally irradiated while magnetic stirring was performed. A400W high-pressure mercury lamp was used as a light source, and a vessel made of borosilicate glass was used as a reaction vessel to irradiate visible light and ultraviolet light. The detection and quantification of the hydrogen and oxygen produced was performed by gas chromatography. The experimental results show that hydrogen is stably produced at 100. mu. mol/h and 80. mu. mol/h, and oxygen is not produced. This indicates that the following reaction occurred: the holes oxidatively decompose methanol and the electrons reduce water to produce hydrogen.
Comparative example 1
In example 1, for NiOx/InTaO not substituted with Ni4And RuO2/InTaO4Was evaluated, but the ratio NiOx/In was determined1-xNixTaO4And RuO2/In1-xNixTaO4The activity of example 1 was low.
Comparative example 2
In the representative photocatalyst Pt-TiO2, there was no reaction under only visible light irradiation.
Table 1: photocatalyst Activity
Example gas generation speed (μmol/h) of semiconductor co-reaction light source
Agent H O
Example In1-xNixTaO4(x 0.05) partial Xe lamps (>420nm) 4.22.1 from NiOx water
17.08.1 solution of 1 (x ═ 0.1)
(x＝0.15 8.3 4.1
) RuO2 Xe lamp (>420nm) 2.01.0
Example In1-xNixTaO4(x ═ 0.05) water fraction 8.74.3
2 (x ═ 0.1) solution 4.82.3
Comparative example InTaO4 partial Xe lamp (>420nm) 3.21.1 with NiOx Water
1 RuO2 solution 0.80.4
TiO2 Pt Xe lamp (>420nm) tr 0
Claims (9)
1. A visible light-responsive photocatalyst characterized by comprising a compound oxide semiconductor comprising indium, an element 5A of the periodic Table of the elements and a transition metal element M, InAO4An oxide semiconductor represented by (A: 5A element) and a chemical formula In which a part of indium is replaced by a transition metal M1-xMxAO4Wherein the sum of the number of moles of indium and M is equal to the number of moles of A, these compound oxide semiconductors are used as a photocatalyst.
2. The visible-light-responsive photocatalyst as set forth in claim 1, wherein A is at least one element selected from Nb, Ta and V, and M is an oxide semiconductor composed of at least one element selected from Cr, Mn, Fe, Co, Ni, Cu and Zn.
3. The visible-light-responsive photocatalyst as claimed in claim 1 or 2, wherein the surface of said compound oxide semiconductor is modified with a conventional Co-catalyst such as Pt, Pd noble metal or Ni, Co transition metal, NiO and IrO2、NiOx、RuO2An oxide.
4. The visible-light-responsive photocatalyst as claimed in claim 3, wherein said co-catalyst is used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight.
5. The visible-light-responsive photocatalyst as set forth In claim 1, wherein the formula In is used1-xNixTaO4Or In1-xNixNbO4。
6. The visible-light-responsive photocatalyst according to claim 2 or 3, wherein the photocatalyst is irradiated with light containing ultraviolet rays and visible light to decompose harmful chemical substances by suspending the photocatalyst in an aqueous solution containing organic substances to irradiate the photocatalyst, or by fixing the photocatalyst on a base, and the liquid is slowly flown on the surface thereof, or by a gas phase reaction in decomposing malodorous substances in a vaporizing chamber.
7. The visible-light-responsive photocatalyst according to claim 2 or 3, wherein the photocatalyst is irradiated with light containing ultraviolet rays and visible light to produce hydrogen, and the reaction is carried out by suspending the photocatalyst in an aqueous solution containing an organic substance and irradiating the catalyst with light, or by fixing the photocatalyst on a base and allowing the liquid to flow gradually over the surface of the photocatalyst.
8. The visible-light-responsive photocatalyst according to claim 2 or 3, wherein the photocatalyst is irradiated with light containing ultraviolet rays or visible light to completely decompose water into hydrogen and oxygen to produce hydrogen, and the reaction is carried out by suspending the catalyst in an aqueous solution containing organic substances and irradiating the solution with light, or by fixing the catalyst on a base and allowing the solution to flow slowly over the surface of the base.
9. The visible-light-responsive photocatalyst as claimed in claim 1 or 2, wherein x of said complex oxide is larger than 0 and smaller than 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101062806A CN1321742C (en) | 2003-11-13 | 2003-11-13 | Visible light response photocatalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101062806A CN1321742C (en) | 2003-11-13 | 2003-11-13 | Visible light response photocatalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1544144A true CN1544144A (en) | 2004-11-10 |
| CN1321742C CN1321742C (en) | 2007-06-20 |
Family
ID=34334065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101062806A Expired - Fee Related CN1321742C (en) | 2003-11-13 | 2003-11-13 | Visible light response photocatalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1321742C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100423293C (en) * | 2006-04-30 | 2008-10-01 | 南京大学 | Solar cell and its preparing method |
| CN102872853A (en) * | 2012-09-26 | 2013-01-16 | 北京工业大学 | Three-dimensional ordered macroporous InVO4 visible light-responsive photocatalyst, preparation and application |
| CN104307527A (en) * | 2014-10-24 | 2015-01-28 | 桂林理工大学 | Visible light responding photocatalyst InFeZn5O8 and preparation method thereof |
| CN104841440A (en) * | 2015-05-07 | 2015-08-19 | 北京化工大学 | Heterojunction type ternary composite semiconductor photocatalyst and preparation method thereof |
| CN106732717A (en) * | 2013-05-31 | 2017-05-31 | 天津大学 | Decomposition water produces application in hydrogen and oxygen to the catalyst being made up of element tantalum indium nickel oxygen and nitrogen under visible light |
| CN107376960A (en) * | 2017-07-11 | 2017-11-24 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of nickel doping phosphoric acid indium photochemical catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151886C (en) * | 2001-12-06 | 2004-06-02 | 中国科学院大连化学物理研究所 | Catalyst for reduction of nitrogen oxide, its preparation method and use |
-
2003
- 2003-11-13 CN CNB2003101062806A patent/CN1321742C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100423293C (en) * | 2006-04-30 | 2008-10-01 | 南京大学 | Solar cell and its preparing method |
| CN102872853A (en) * | 2012-09-26 | 2013-01-16 | 北京工业大学 | Three-dimensional ordered macroporous InVO4 visible light-responsive photocatalyst, preparation and application |
| CN106732717A (en) * | 2013-05-31 | 2017-05-31 | 天津大学 | Decomposition water produces application in hydrogen and oxygen to the catalyst being made up of element tantalum indium nickel oxygen and nitrogen under visible light |
| CN106732717B (en) * | 2013-05-31 | 2019-03-05 | 天津大学 | Application in water generation hydrogen and oxygen is decomposed by the catalyst that element tantalum indium nickel oxygen and nitrogen form under visible light |
| CN104307527A (en) * | 2014-10-24 | 2015-01-28 | 桂林理工大学 | Visible light responding photocatalyst InFeZn5O8 and preparation method thereof |
| CN104841440A (en) * | 2015-05-07 | 2015-08-19 | 北京化工大学 | Heterojunction type ternary composite semiconductor photocatalyst and preparation method thereof |
| CN104841440B (en) * | 2015-05-07 | 2017-12-12 | 北京化工大学 | A kind of heterojunction type tri compound semiconductor light-catalyst and preparation method thereof |
| CN107376960A (en) * | 2017-07-11 | 2017-11-24 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of nickel doping phosphoric acid indium photochemical catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1321742C (en) | 2007-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Novel 3DOM-SrTiO3/Ag/Ag3PO4 ternary Z-scheme photocatalysts with remarkably improved activity and durability for contaminant degradation | |
| Mohamed et al. | Enhanced CO2 photocatalytic conversion into CH3OH over visible‐light‐driven Pt nanoparticle-decorated mesoporous ZnO–ZnS S-scheme heterostructures | |
| Zhou et al. | Fabrication and photoelectrocatalytic properties of nanocrystalline monoclinic BiVO4 thin-film electrode | |
| Teixeira et al. | SrSnO3 perovskite obtained by the modified Pechini method—insights about its photocatalytic activity | |
| CN105521800A (en) | Ultrathin BiOBrxI1-x photocatalyst and preparation method thereof | |
| CN1799690A (en) | Visible light responsible photocatalysis material of AgTO2 type composite oxide and its application | |
| CN110951088A (en) | Zirconium-based metal organic framework material, preparation and application as chromium removal agent | |
| JP4000374B2 (en) | Semiconductor metal oxide photocatalyst and method for decomposing hazardous chemicals using the same | |
| JP3742873B2 (en) | Photocatalyst, method for producing hydrogen using the same, and method for decomposing toxic substances | |
| JP3890414B2 (en) | Perovskite complex oxide visible light responsive photocatalyst, hydrogen production method using the same, and hazardous chemical decomposition method | |
| Kavil et al. | Efficient photocatalytic reduction of CO 2 present in seawater into methanol over Cu/C-Co-doped TiO 2 nanocatalyst under UV and natural sunlight | |
| Kumar et al. | Epigrammatic status and perspective of sequestration of carbon dioxide: Role of TiO2 as photocatalyst | |
| Imranullah et al. | Stable and highly efficient natural sunlight driven photo-degradation of organic pollutants using hierarchical porous flower-like spinel nickel cobaltite nanoflakes | |
| Hu et al. | Synthesis and characterization of graphene oxide-modified Bi 2 WO 6 and its use as photocatalyst | |
| Brillas et al. | Removal of paracetamol (acetaminophen) by photocatalysis and photoelectrocatalysis. A critical review | |
| CN1905940A (en) | Photocatalyst based on composite oxide responsive to visible light and method for decomposition and removal of harmful chemical material using the same | |
| CN1544144A (en) | Visible light response photocatalyst and application thereof | |
| JP3735711B2 (en) | Visible light-responsive rare earth compound photocatalyst, hydrogen production method using the same, and hazardous chemical decomposition method | |
| JP3834625B2 (en) | Indium barium composite oxide visible light responsive photocatalyst, method for producing hydrogen using this photocatalyst, and method for decomposing harmful chemical substances | |
| Li et al. | Current progress on persistent fluorescence-assisted composite photocatalysts | |
| Alsolami et al. | Efficient visible-light photooxidation of ciprofloxacin antibiotic over CoTiO3-impregnated 2D CeO2 nanocomposites synthesized by a sol-gel-based process | |
| JP3718710B2 (en) | Visible light responsive photocatalyst, hydrogen production method using the same, and hazardous chemical decomposition method | |
| JP4296259B2 (en) | Method for producing hydrogen | |
| Lim et al. | Synthesis of Hybrid Cu-Doped TiO2 Photocatalyst for Dye Removal | |
| JP3903179B2 (en) | Indium complex oxide visible light responsive photocatalyst and oxidative decomposition method of materials using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |