阅读说明：本技术 一种石墨烯掺杂Ag/TiO2光催化涂层及其制备方法 (A kind of graphene doping Ag/TiO2Photocatalysis coating and preparation method thereof ) 是由 简明德 练国富 刘成武 书铁平 于 2019-09-18 设计创作，主要内容包括：本发明公开一种石墨烯掺杂Ag/TiO_2光催化涂层及其制备方法,1)对工件进行预处理；2)制备石墨烯掺杂Ag/TiO_2复合浆料；3)将浆料通过机械滚轮压制在预处理后的工件表面上,形成基层；4)采用真空感应烧结法,将形成基层后的工件置于烧结模具中,烧结后在工件表面形成预置层；5)将带有预置层的工件置于激光加工设备中进行激光熔覆,即得石墨烯掺杂Ag/TiO_2光催化涂层。本发明方法提供的石墨烯掺杂Ag/TiO_2光催化涂层,能够解决缩短催化剂的禁带宽度使吸收光谱向可见光扩展来提高太阳能利用率的问题。本发明充分利用掺杂物的性质,增强三组分的协同效应,提高复合材料的光催化性能,增加对污染物的降解效率。(The present invention discloses a kind of graphene doping Ag/TiO 2 Photocatalysis coating and preparation method thereof, 1) workpiece is pre-processed；2) graphene doping Ag/TiO is prepared 2 Composite mortar；3) slurry is compressed on pretreated workpiece surface by mechanical rollers, forms base；4) vacuum induction sintering process is used, the workpiece after formation base is placed in sintering mold, forms initialization layer in workpiece surface after sintering；5) workpiece with initialization layer is placed in laser process equipment and carries out laser melting coating to get graphene doping Ag/TiO 2 Photocatalysis coating.The graphene that the method for the present invention provides adulterates Ag/TiO 2 Photocatalysis coating, the forbidden bandwidth for being able to solve shortening catalyst make absorption spectrum to visible light extension come the problem of improving solar energy utilization ratio.The present invention makes full use of the property of dopant, enhances the synergistic effect of three components, improves the photocatalysis performance of composite material, increases the degradation efficiency to pollutant.)

1. a kind of graphene adulterates Ag/TiO₂The preparation method of photocatalysis coating, it is characterised in that: itself the following steps are included:

1) workpiece is pre-processed, cleans up the dust, grease and corrosion of workpiece surface；

2) graphene doping Ag/TiO is prepared₂Composite mortar；

3) above-mentioned slurry is compressed on pretreated workpiece surface by mechanical rollers, forms base；

4) vacuum induction sintering process is used, the workpiece after formation base is placed in graphite integral forming sintering mold, is sintered Initialization layer is formed in workpiece surface afterwards；

5) workpiece with initialization layer is placed in laser process equipment and carries out laser melting coating to get graphene doping Ag/TiO₂Light Catalyst coatings.

2. a kind of graphene according to claim 1 adulterates Ag/TiO₂The preparation method of photocatalysis coating, it is characterised in that: In step 1), workpiece surface is polished in advance, and is aided with the greasy dirt of acetone and washes of absolute alcohol removing substrate surface.

3. a kind of graphene according to claim 1 adulterates Ag/TiO₂The preparation method of photocatalysis coating, it is characterised in that: Graphene described in step 2 adulterates Ag/TiO₂Composite mortar the preparation method is as follows: by graphene powder, Ag, TiO₂By mass parts It is put into ball milling 2-2.5h in ball mill after number mixing, adhesive solution is then added and uniformly mixes, obtains graphene doping Ag/ TiO₂Composite mortar.

4. a kind of graphene according to claim 3 adulterates Ag/TiO₂The preparation method of photocatalysis coating, it is characterised in that: The graphene powder, Ag, TiO₂Mass ratio be 1:3:16.

5. a kind of graphene according to claim 3 adulterates Ag/TiO₂The preparation method of photocatalysis coating, it is characterised in that: The adhesive solution is the polyvinyl alcohol water solution or epoxy polyester powdery paints that mass percent is 3- 5%.

6. a kind of graphene according to claim 1 adulterates Ag/TiO₂The preparation method of photocatalysis coating, it is characterised in that: The technological parameter of sintering described in step 4) is as follows: 10~50kW of heating power, 10~30 DEG C/min of heating rate, sintering temperature 980~1200 DEG C, 200~400 DEG C of substrate preheating temperature, 20~360min of peak temperature soaking time.

7. a kind of graphene according to claim 1 adulterates Ag/TiO₂The preparation method of photocatalysis coating, it is characterised in that: The technological parameter of laser melting coating described in step 5) is as follows: laser beam power 130-170W, scanning speed 800-1200 mm/s, Sweep span 0.04-0.08mm, 20-50 μm of powdering thickness, spot diameter 0.05-0.15mm, argon gas 100-300ppm, overlap joint 10~80 μm of rate, forming kenel is parallel or 45 degree of oblique angle.

8. the graphene that -7 either method obtain according to claim 1 adulterates Ag/TiO photocatalysis coating.

Technical field

The present invention relates to photocatalysis coating fields more particularly to a kind of graphene to adulterate Ag/TiO₂Photocatalysis coating and its Preparation method.

Background technique

In recent years, there is potential application value in every field due to photochemical catalyst, researcher is in Development of Novel light Huge effort has been paid in terms of catalyst.Titanium dioxide is a kind of nontoxic catalysis material from a wealth of sources, with Other semiconductor catalysis materials (CdS, SnO, ZnO, ZnS etc.) are compared, and photochemical properties are more stable, have higher urge Change efficiency and Strong oxdiative ability, comprehensively considers the factor of various aspects, TiO₂ , degradation strong with oxidability completely and can repeat The advantages that use, sewage treatment, photoelectric conversion, cleaning material in terms of be concerned.TiO₂Because of its own nothing The features such as malicious, cheap, non-corrosive, wide spectrum strong applicability, photocatalytic activity are high, chemical property is stablized and become vast scientific work The catalysis material of author's popular research；More because it can be reused, thereby increases and it is possible to directly using solar source as reaction light The features such as source and be widely used in photocatalysis degradation organic contaminant, be a kind of green with broad based growth and Utilization prospects Environmental improvement material has become the photochemical catalyst for most having application prospect.But TiO₂Greater band gap (about 3.2eV), Zhi Neng Ultra-violet (UV) band of the wavelength less than 378 nm shows photochemical activity, to the utilization rate of solar energy less than 10%, while its light induced electron Be easy to happen with hole compound, and there is photooxidation, to reduce photocatalysis efficiency, this property make its promote and apply by To limitation.Doping is such as metal ion, anion, different semiconductors couplings and the methods of noble metal decorated improves spectral response red shift A kind of effective way, especially shallow level impurity doping is easier to move on to spectral response visible light even near infrared range, Noble metal, transition metal, rare earth metal and lanthanide series metal etc. adulterate the heterojunction photocatalyst of TiO2 formation to photocatalytic water system The reaction systems such as hydrogen, light degradation organic matter, CO methanation and the synthesis of selective organic-fuel have excellent photocatalytic activity and Stability.Relative to pure TiO₂The purposes of photochemical catalyst is more extensive, cannot be only used for the pollutant in photocatalytic degradation water, Also act as the filler of photodegradation film, antibiotic paint etc..Therefore, how by adulterating TiO is improved₂ Photocatalytic activity is Study the practical key of its photocatalysis technology.Metal/non-metal doping is the band-gap energy and raising light energy absorption for reducing TiO 2 One of important channel of ability.

Noble metal granule and semiconductor contact interface, which will form Schottky barrier, migrates electronics from semiconductor to metal, suppression Electrons and holes processed it is compound；The plasma resonance effect of precious metal surface can also enhance the absorption to visible light, to expand TiO₂Optical response range.Silver material is widely used in multiple fields as excellent inorganic antiseptic, while being also one The important inorganic photosensitive agent material of kind.Compared to noble metals such as Pt, Au and Rh, by the structure, the ruler that control Nano silver grain Very little, shape etc. adjusts plasma resonance wavelength and the strength of resonance, so that the response range of photochemical catalyst absorbing wavelength is widened, it is real Now to the effective use of visible light.Ag is easier that oxidation and reduction reaction occurs during the preparation process, is more advantageous to nano particle Formation, and the price of Ag is more cheap, is more suitable for practical application.

Graphene is a kind of two-dimentional graphite material of novel monoatomic thickness, and specific surface area is up to 2600 m²/ g, Its special two-dimension plane structure and the pi-conjugated system of π-have stronger suction-operated to dyestuff, make dye molecule and are supported on The semiconductor light-catalyst on the surface GO comes into full contact with, and is easier to carry out photocatalytic process.Secondly, its good electric conductivity and Chemical stability, allows to serve as the bridge of electron transmission, reduces the compound of semiconductor light-catalyst light induced electron and hole Probability, to increase the photoelectric activity of photochemical catalyst.Meanwhile graphene plays the role of doping in the composite, will reduce by half The forbidden bandwidth of conductor photochemical catalyst reinforces compound in the photocatalysis performance of visible light region.

Summary of the invention

For existing pure TiO₂ There are catalyst quantum low yield and band gap it is wide caused by optic response range it is relatively narrow, Its application in actual production can only be limited by ultraviolet excitation, the defects such as low to solar energy utilization ratio, the present invention mentions Ag/TiO is adulterated for a kind of graphene₂Photocatalysis coating and preparation method thereof, the forbidden bandwidth for solving to shorten catalyst make to absorb Spectrum is to visible light extension come the problem of improving solar energy utilization ratio.

In order to achieve the above object, the invention adopts the following technical scheme:

A kind of graphene doping Ag/TiO₂The preparation method of photocatalysis coating comprising following steps:

1) workpiece is pre-processed, cleans up the dust, grease and corrosion of workpiece surface；

2) graphene doping Ag/TiO is prepared₂Composite mortar；

3) above-mentioned slurry is compressed on pretreated workpiece surface by mechanical rollers, forms base；

4) vacuum induction sintering process is used, the workpiece after formation base is placed in graphite integral forming sintering mold, is sintered Initialization layer is formed in workpiece surface afterwards；

5) workpiece with initialization layer is placed in laser process equipment and carries out laser melting coating to get graphene doping Ag/TiO₂ Photocatalysis coating.

In step 1), workpiece surface is polished in advance, and is aided with acetone and washes of absolute alcohol removing substrate surface Greasy dirt.

Graphene described in step 2 adulterates Ag/TiO₂Composite mortar the preparation method is as follows: by graphene powder, Ag, TiO₂ It is put into ball milling 2-2.5 h in ball mill after mixing by mass fraction, adhesive solution is then added and uniformly mixes, obtains graphene Adulterate Ag/TiO₂Composite mortar.

Further, the graphene powder, Ag, TiO₂Mass ratio be 1:3:16.

The adhesive solution is the polyvinyl alcohol water solution or epoxy polyester powdery paints that mass percent is 3- 5%.

The technological parameter of sintering described in step 4) is as follows: 10~50kW of heating power, 10~30 DEG C/min of heating rate, 980~1200 DEG C of sintering temperature, 200~400 DEG C of substrate preheating temperature, 20~360min of peak temperature soaking time.

The technological parameter of laser melting coating described in step 5) is as follows: laser beam power 130-170W, scanning speed 800- 1200 mm/s, sweep span 0.04-0.08mm, 20-50 μm of powdering thickness, spot diameter 0.05-0.15mm, argon gas 100- 300ppm, 10~80 μm of overlapping rate, forming kenel is parallel or 45 degree of oblique angle.

The invention adopts the above technical scheme, with other TiO₂Photocatalysis coating is compared with following advantages and beneficial to effect Fruit: graphene doping Ag/TiO is prepared using heating in vacuum sintering process₂ Composite coating is toxic useless for photocatalytic degradation Gas -- toluene.Ag/TiO is adulterated in graphene₂In mixed system, Ag has the spies such as nontoxic, cheaper, modified effect be obvious TiO can be improved by adulterating Ag in point₂Catalytic activity.Graphene is introduced, because graphene has biggish specific surface area simultaneously And surface possesses more pi-electron and can adsorb more toluene with toluene molecule generation pi-pi bond conjugation and divide Son, and the doping of graphene can significantly improve the photocatalytic activity of composite material.Under visible light conditions, graphene doping Ag/TiO₂Composite material is much higher than pure TiO to the degradation rate of toluene₂.Graphene proposed by the present invention adulterates Ag/TiO₂Powder is multiple Condensation material can make full use of the property of dopant, enhance the synergistic effect of three components, improve the photocatalytic of composite material Can, increase the degradation efficiency to pollutant, the organic pollutant in waste water can not only be degraded by catalytic to H₂O and CO₂, to air In such as formaldehyde, toluene effumability organic pollutant equally there is preferable degradation effect.The present invention has very strong visible Photoresponse enhances visible light chemical reaction using the slow photon effect of photonic crystal, and out-phase structure is conducive to photo-generated carrier Separation, improve visible light catalytic ability.

The present invention can be used for photocatalysis degradation organic contaminant and light urged under conditions of visible light and sunlight are light source Change hydrogen production by water decomposition, is also directly applicable to weaving, glass with clean, suncream, coating, ink, packaging material for food, paper maker In industry, aerospace industry, in lithium battery, have broad application prospects.

Specific embodiment

A kind of graphene doping Ag/TiO₂The preparation method of photocatalysis coating, comprising the following steps:

1) it after the dust for cleaning up workpiece surface, is polished in advance workpiece surface, and is aided with acetone and dehydrated alcohol is clear Remove the greasy dirt for removing substrate surface；

2) graphene doping Ag/TiO is prepared₂Composite mortar: by graphene powder, Ag, TiO₂It is mixed in mass ratio for 1:3:16 After be put into ball milling 2-2.5 h in ball mill, then be added adhesive solution uniformly mix, obtain graphene doping Ag/TiO₂It is multiple Close slurry；

The adhesive solution is the polyvinyl alcohol water solution or epoxy polyester powdery paints that mass percent is 3- 5%；

3) above-mentioned slurry is compressed on pretreated workpiece surface by mechanical rollers, forms base；

4) vacuum induction sintering process is used, the workpiece after formation base is placed in graphite integral forming sintering mold, is sintered Initialization layer is formed in workpiece surface afterwards, the technological parameter of the sintering is as follows: 10~50kW of heating power, heating rate 10~ 30 DEG C/min, 980~1200 DEG C of sintering temperature, 200~400 DEG C of substrate preheating temperature, peak temperature soaking time 20~ 360min；

5) workpiece with initialization layer is placed in laser process equipment and carries out laser melting coating to get graphene doping Ag/TiO₂ The technological parameter of photocatalysis coating, the laser melting coating is as follows: laser beam power 130-170W, scanning speed 800-1200 Mm/s, sweep span 0.04-0.08mm, 20-50 μm of powdering thickness, spot diameter 0.05-0.15mm, argon gas 100-300ppm, 10~80 μm of overlapping rate, forming kenel is parallel or 45 degree of oblique angle.