CN101530789B - Nanometer titanium dioxide compound photocatalyst and preparation method thereof - Google Patents
Nanometer titanium dioxide compound photocatalyst and preparation method thereof Download PDFInfo
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- CN101530789B CN101530789B CN2009100493949A CN200910049394A CN101530789B CN 101530789 B CN101530789 B CN 101530789B CN 2009100493949 A CN2009100493949 A CN 2009100493949A CN 200910049394 A CN200910049394 A CN 200910049394A CN 101530789 B CN101530789 B CN 101530789B
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Abstract
A nanometer titanium dioxide compound photocatalyst and a preparation method thereof belong to the technical field of sewage disposal, the catalyst comprises the components as follows according to mass percentage: 60-99.5% of nanometer titanium dioxide particle and 40-0.5% of gold nanoparticle, wherein, the particle size of the nanometer titanium dioxide particle is 10-80nm, the gold nanoparticle with the particle size of 5-10nm adheres to the surface of the nanometer titanium dioxide particle. The invention adopts nanometer titanium dioxide particle and the chloroauric acid particle as raw materials, makes use of the weak reducibility of urea to prepare the compound photocatalyst which has a good visible light response, thus degrading sulfur-containing organic pollutant by photocatalysis excellently and having excellent practicability.
Description
Technical field
What the present invention relates to is a kind of Catalysts and its preparation method of technical field of sewage, specifically is a kind of nanometer titanium dioxide compound photocatalyst and preparation method thereof.
Background technology
Since last century, along with the quickening of process of industrialization, the application of organic dyestuff more and more widely.In use require the good stability of organic dyestuff, but when such organic consumption is abundant, because difficult degradation makes it easily in the occurring in nature enrichment, and through various channels, particularly the food chain of the ecosystem enters human body through transmitting, the life and health of harm humans, inducements such as the animal kingdom and the mankind's the phenomenon of feminizing, cancer high incidence mainly come from these persistence organic pollutants in recent years, are referred to as POPs (Persistent Organic Pollutants) in the world.In electronics industry, improve electroplating efficiency, improve electroplating effect, yet after the form with waste water is discharged in the nature system, bring serious harm equally for the ecosystem as often using the sulfur-bearing type organic in the galvanizing process of conventional project.For these organic pollutant wastewaters, people have worked out multiple advanced means and have handled, the current senior oxidation technologies such as ultra-violet radiation, ozone, Fenton's reaction and photocatalysis that generally adopt.By these methods, the organic matter of complex structure, difficult degradation or bio-transformation can be handled to a certain extent, wait shortcomings such as cost costliness but often have power consumption.Comparatively speaking, photocatalysis technology wherein has bigger potential application foreground.When particularly utilizing nano titanium oxide as photochemical catalyst, higher with its oxidation activity, chemical stability good, cost is low, advantage such as pollution-free is paid attention to most, being present most widely used nano-photocatalyst material, also is the environmental type catalyst that has the exploitation future most.But it moves towards real application as photochemical catalyst and still has certain difficulty, and one of them important bottleneck problem is exactly the restriction of excitation wavelength.Because the energy gap of titanium dioxide is 3.2eV, require its corresponding excitation wavelength should be less than 387nm, belong to ultraviolet region (ultraviolet light contains quantity not sufficient 5% in solar energy), from utilizing the angle of solar energy, the photochemical catalyst of most economical practicality should be able to utilize visible light part abundant in the sunshine, and substitutes expensive artificial light source with this.Therefore how utilizing the excitation source of visible light conduct to become most important problem in the present photocatalysis research, will be one of important channel that solves these class methods and have visible light corresponding light Preparation of catalysts.Core process in the photocatalysis treatment technology---pollutant is in degraded of catalyst surface---is an interfacial chemical reaction in addition, when pollutant can effectively improve catalytic efficiency easily when catalyst surface absorption is strong, so the characteristic of catalyst surface is played the part of this important role in Application of Catalyst.In current patent of having applied for, do not see that relevant titania-based composite nano-catalyst is used for the related content that the sulfur-bearing organic pollution is handled.
Scientific research simultaneously shows, golden nanometer particle have visible absorption and to sulphur have high affinity etc. be characterized as its load on the titanium dioxide nanoparticle surface preparation can handle effectively that the processing of sulfurous organic compound contaminant water provides may.And the preparation of this kind composite photocatalyst will provide new means for the processing of sulfur-bearing type organic pollutant effluents.Therefore invent a kind of straightforward procedure for preparing such catalyst for handling industrial pollution waste water, improving environment for human survival and have crucial society and economic worth.
Patent documentation yet there are no similar nanometer titanium dioxide compound photocatalyst preparation method report by retrieval.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of nanometer titanium dioxide compound photocatalyst and preparation method thereof is provided, by nano TiO 2 powder is mixed with chlorauric acid solution, condensing reflux under the condition of adding urea liquid constant temperature heating bath obtains having visible light-responded composite Nano photochemical catalyst through processing such as deionized-distilled water cleaning and heat dryings afterwards.
The present invention is achieved by the following technical solutions, the component and the mass percent thereof that the present invention relates to nanometer titanium dioxide compound photocatalyst are: 60%～99.5% titanium dioxide nanoparticle and 40%～0.5% gold chloride particle, wherein: the particle diameter of titanium dioxide nanoparticle is 10～80nm, is the gold chloride particle of 5～10nm at titanium dioxide nanoparticle surface attachment particle diameter.
The present invention relates to the preparation method of nanometer titanium dioxide compound photocatalyst, specifically may further comprise the steps:
The first step, get titanium dioxide nanoparticle and add chlorauric acid solution and mix;
The concentration of described chlorauric acid solution is 5～20g/L;
The particle diameter of described titanium dioxide nanoparticle is 10～80nm, and the consumption of this titanium dioxide granule and the mass ratio of chlorauric acid solution are 4: 1～9: 1.
Second the step, further in chlorauric acid solution, add urea liquid, condensing reflux was made nano suspending liquid in 4～10 hours under 70 ℃～110 ℃ conditions then;
The concentration of described urea liquid is 0.6Mol/L.
The 3rd goes on foot, nano suspending liquid employing deionized water is washed, and carries out drying then and handle under isoperibol, and the nano suspending liquid after at last drying being handled is cooled to room temperature and makes nanometer titanium dioxide compound photocatalyst.
Described deionized water washs and is meant with deionized-distilled water washing nano suspending liquid totally 3 times.
Carry out dry the processing under the described isoperibol and be meant under 105 ℃ condition freeze-day with constant temperature 24 hours.
The present invention is by mixing titanium dioxide nanoparticle suitability for industrialized production, that have catalytic activity (the anatase crystalline form is main) and chlorauric acid solution, condensing reflux under the condition of adding urea liquid constant temperature heating bath obtains having visible light-responded composite Nano photochemical catalyst through processing such as deionized-distilled water cleaning and heat dryings afterwards.
The present invention has following advantage: (1) makes that final nanometer visible-light photocatalyst specific area is big, catalytic activity good owing to select the titanium dioxide nanoparticle of good uniformity for use, can effectively improve material and light utilization ratio; (2) utilize the visible light absorption of golden nanometer particle, can well utilize the solar energy that is mainly the visible light composition; (3) utilize the characteristic of gold, accelerated of the absorption of sulfur-bearing organic pollution, accelerated the speed of photocatalysis treatment sewage greatly at catalyst surface to the sulphur high affinity; (4) this Preparation of catalysts process is simple, green, does not produce secondary pollution.
The present invention uses titanium dioxide nanoparticle and chlorauric acid solution as raw material first, and the composite photo-catalyst that utilizes the week reduction of urea to make is visible light-responded good, can be good at photocatalytic degradation sulfur-bearing organic pollution, has good practicability.
Description of drawings
Fig. 1 is the TEM photo of the nanometer titanium dioxide compound photocatalyst that synthesized of embodiment 1
The specific embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
Take by weighing commercial titanium dioxide nanoparticle 4.5 grams that are of a size of 50nm, adding mass percent concentration is the chlorauric acid solution 100mL of 5g/L, and the titanium dioxide granule wherein and the mass ratio of gold chloride are 90: 10, then chlorauric acid solution are mixed; Add the urea liquid that concentration is 0.6Mol/L again, mix well the back under 80 ℃ of conditions condensing reflux 8 hours until forming pink suspension; Wash above-mentioned suspension 3 times with deionized-distilled water; Freeze-day with constant temperature is 24 hours under 105 ℃ of conditions, is cooled to room temperature and obtains the light red pressed powder, and it is standby to make nanometer titanium dioxide compound photocatalyst.
As shown in Figure 1, the TEM photo of the nanometer titanium dioxide compound photocatalyst for preparing for present embodiment, formed the gold nano grain of about 5nm as can be seen on random titanium dioxide nanoparticle surface, wherein the mass ratio of nanometer titanium dioxide carbon granule and gold nano grain is 200: 1.
Embodiment 2:
Take by weighing commercial titanium dioxide nanoparticle 3.0 grams that are of a size of 50nm, adding mass percent concentration is the chlorauric acid solution 100mL of 20g/L, and the titanium dioxide granule wherein and the mass ratio of gold chloride are 60: 40, then chlorauric acid solution are mixed; Add the urea liquid that concentration is 0.6Mol/L again, mix well the back under 80 ℃ of conditions condensing reflux 8 hours until forming pink suspension; Wash above-mentioned suspension 3 times with deionized-distilled water; Freeze-day with constant temperature is 24 hours under 105 ℃ of conditions, is cooled to the nanometer titanium dioxide compound photocatalyst that room temperature obtains the light red solid, and wherein the mass ratio of nanometer titanium dioxide carbon granule and gold nano grain is 200: 1.
Embodiment 3:
Take by weighing commercial titanium dioxide nanoparticle 3.0 grams that are of a size of 50nm, adding mass percent concentration is the chlorauric acid solution 100mL of 20g/L, and the titanium dioxide granule wherein and the mass ratio of gold chloride are 60: 40, then chlorauric acid solution are mixed; Add the urea liquid that concentration is 0.6Mol/L again, mix well the back under 80 ℃ of conditions condensing reflux 8 hours until forming pink suspension; Wash above-mentioned suspension 3 times with deionized-distilled water; Freeze-day with constant temperature is 24 hours under 105 ℃ of conditions, is cooled to the nanometer titanium dioxide compound photocatalyst that room temperature obtains the light red solid, and wherein the mass ratio of nanometer titanium dioxide carbon granule and gold nano grain is 10: 3.
Embodiment 4:
Take by weighing commercial titanium dioxide nanoparticle 4.0 grams that are of a size of 50nm, adding mass percent concentration is the chlorauric acid solution 100mL of 10g/L, and the titanium dioxide granule wherein and the mass ratio of gold chloride are 40: 10, then chlorauric acid solution are mixed; Add the urea liquid that concentration is 0.6Mol/L again, mix well the back under 80 ℃ of conditions condensing reflux 8 hours until forming pink suspension; Wash above-mentioned suspension 3 times with deionized-distilled water; Freeze-day with constant temperature is 24 hours under 105 ℃ of conditions, is cooled to the nanometer titanium dioxide compound photocatalyst that room temperature obtains the light red solid, and wherein the mass ratio of nanometer titanium dioxide carbon granule and gold nano grain is 10: 1.
Embodiment 5:
Take by weighing commercial titanium dioxide nanoparticle 4.5 grams that are of a size of 50nm, adding mass percent concentration is the chlorauric acid solution 100mL of 5g/L, and the titanium dioxide granule wherein and the mass ratio of gold chloride are 90: 10, then chlorauric acid solution are mixed; Add the urea liquid that concentration is 0.6Mol/L again, mix well the back under 70 ℃ of conditions condensing reflux 10 hours until forming pink suspension; Wash above-mentioned suspension 3 times with deionized-distilled water; Freeze-day with constant temperature is 24 hours under 105 ℃ of conditions, is cooled to the nanometer titanium dioxide compound photocatalyst that room temperature obtains the light red solid, and wherein the mass ratio of nanometer titanium dioxide carbon granule and gold nano grain is 200: 1.
Embodiment 6:
Take by weighing commercial titanium dioxide nanoparticle 4.5 grams that are of a size of 50nm, adding mass percent concentration is the chlorauric acid solution 100mL of 5g/L, and the titanium dioxide granule wherein and the mass ratio of gold chloride are 90: 10, then chlorauric acid solution are mixed; Add the urea liquid that concentration is 0.6Mol/L again, mix well the back under 110 ℃ of conditions condensing reflux 4 hours until forming pink suspension; Wash above-mentioned suspension 3 times with deionized-distilled water; Freeze-day with constant temperature is 24 hours under 105 ℃ of conditions, is cooled to the nanometer titanium dioxide compound photocatalyst that room temperature obtains the light red solid, and wherein the mass ratio of nanometer titanium dioxide carbon granule and gold nano grain is 200: 1.
Embodiment 7:
Take by weighing commercial titanium dioxide nanoparticle 4.5 grams that are of a size of 50nm, adding mass percent concentration is the chlorauric acid solution 100mL of 5g/L, and the titanium dioxide granule wherein and the mass ratio of gold chloride are 90: 10, then chlorauric acid solution are mixed; Add the urea liquid that concentration is 0.6Mol/L again, mix well the back under 90 ℃ of conditions condensing reflux 6 hours until forming pink suspension; Wash above-mentioned suspension 3 times with deionized-distilled water; Freeze-day with constant temperature is 24 hours under 105 ℃ of conditions, is cooled to the nanometer titanium dioxide compound photocatalyst that room temperature obtains the light red solid, and wherein the mass ratio of nanometer titanium dioxide carbon granule and gold nano grain is 200: 1.
Embodiment 8:
Take by weighing and be of a size of commercial titanium dioxide nanoparticle 4.5 grams of 10nm, adding mass percent concentration is the chlorauric acid solution 100mL of 5g/L, and the titanium dioxide granule wherein and the mass ratio of gold chloride are 90: 10, then chlorauric acid solution are mixed; Add the urea liquid that concentration is 0.6Mol/L again, mix well the back under 80 ℃ of conditions condensing reflux 8 hours until forming pink suspension; Wash above-mentioned suspension 3 times with deionized-distilled water; Freeze-day with constant temperature is 24 hours under 105 ℃ of conditions, is cooled to the nanometer titanium dioxide compound photocatalyst of making that room temperature obtains the light red solid, and wherein the mass ratio of nanometer titanium dioxide carbon granule and gold nano grain is 200: 1.
Embodiment 9:
Take by weighing and be of a size of commercial titanium dioxide nanoparticle 4.5 grams of 80nm, adding mass percent concentration is the chlorauric acid solution 100mL of 5g/L, and the titanium dioxide granule wherein and the mass ratio of gold chloride are 90: 10, then chlorauric acid solution are mixed; Add the urea liquid that concentration is 0.6Mol/L again, mix well the back under 80 ℃ of conditions condensing reflux 8 hours until forming pink suspension; Wash above-mentioned suspension 3 times with deionized-distilled water; Freeze-day with constant temperature is 24 hours under 105 ℃ of conditions, is cooled to the nanometer titanium dioxide compound photocatalyst that room temperature obtains the light red solid, and wherein the mass ratio of nanometer titanium dioxide carbon granule and gold nano grain is 200: 1.
Claims (1)
1. the preparation method of a nanometer titanium dioxide compound photocatalyst is characterized in that, may further comprise the steps:
The first step, get titanium dioxide nanoparticle and add chlorauric acid solution and mix;
The concentration of described chlorauric acid solution is 5～20g/L;
The particle diameter of described titanium dioxide nanoparticle is 10～80nm, and the consumption of this titanium dioxide granule and the mass ratio of chlorauric acid solution are 4: 1～9: 1;
Second the step, further in chlorauric acid solution, add urea liquid, condensing reflux was made nano suspending liquid in 4～10 hours under 70 ℃～110 ℃ conditions then;
The 3rd goes on foot, nano suspending liquid employing deionized water is washed, and carries out drying then and handle under isoperibol, and the nano suspending liquid after at last drying being handled is cooled to room temperature and makes nanometer titanium dioxide compound photocatalyst;
Described deionized water washs and is meant with deionized-distilled water washing nano suspending liquid totally 3 times;
Carry out dry the processing under the described isoperibol and be meant under 105 ℃ condition freeze-day with constant temperature 24 hours.
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| CN102220039B (en) * | 2011-04-26 | 2012-10-10 | 福州大学 | Interior photocatalytic coating, preparation method and application thereof |
| CN105014093B (en) * | 2015-01-09 | 2017-07-28 | 宁波工程学院 | The preparation method of the carbon nano-particle of visible ray supporting Pt |
| CN105126888B (en) * | 2015-10-09 | 2018-01-23 | 重庆文理学院 | One kind is used for light-catalysed gold and loads bismuthyl carbonate material and preparation method |
| CN115814816B (en) * | 2022-12-27 | 2024-02-13 | 浙江理工大学 | Transition metal M-Au/TiO2 composite photocatalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547823A (en) * | 1993-06-28 | 1996-08-20 | Ishihara Sangyo Kaisha, Ltd. | Photocatalyst composite and process for producing the same |
| CN1990102A (en) * | 2005-12-30 | 2007-07-04 | 河南大学 | Au/TiO2 catalyst for eliminating ozone by photocatalysis |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547823A (en) * | 1993-06-28 | 1996-08-20 | Ishihara Sangyo Kaisha, Ltd. | Photocatalyst composite and process for producing the same |
| CN1990102A (en) * | 2005-12-30 | 2007-07-04 | 河南大学 | Au/TiO2 catalyst for eliminating ozone by photocatalysis |
Non-Patent Citations (2)
| Title |
|---|
| 李兰廷等.负载型Au/TiO2催化剂的研制及其性能研究.研发前沿.2008,16(5),第23-26页. * |
| 李晓倩等.Au改性TiO2纳米粒子的制备及其光催化活性.哈尔滨工业大学学报.2004,36(10),第1368-1371页. * |
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