CN103801294B - A kind of activated carbon-loaded cuprous oxide photocatalyst and method thereof - Google Patents
A kind of activated carbon-loaded cuprous oxide photocatalyst and method thereof Download PDFInfo
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- CN103801294B CN103801294B CN201410064521.3A CN201410064521A CN103801294B CN 103801294 B CN103801294 B CN 103801294B CN 201410064521 A CN201410064521 A CN 201410064521A CN 103801294 B CN103801294 B CN 103801294B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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Abstract
Activated carbon-loaded cuprous oxide photocatalyst provided by the invention can be used as the photochemical catalyst of the degraded of the organic pollutions such as phenols, purification of air and alkene epoxidation organic synthesis; it is with the active carbon of surface modification and Room Temperature Solid State copper sulphate and NaOH having concurrently under protectant initator effect on a small quantity, by C
6o
12o
6there is Room Temperature Solid State self-propagating reaction and be prepared from reduction.The preparation of activated carbon-loaded cuprous oxide visible-light photocatalyst take copper sulphate as raw material, take active carbon as carrier, at room temperature with solid phase self-propagating reaction, cuprous oxide is downloaded on active carbon, method for preparing catalyst is easy, economy, good stability, photocatalytic activity be high.With the epoxidation organic synthesis of waste water, indoor aldehydes purification of air and the alkene such as this catalyst oxidation phenols, directly can carry out under ultraviolet-visible optical condition, be easy to operation, reaction condition is gentle, and the clearance of pollutant is high, selective good in organic synthesis.
Description
Technical field
The present invention relates to a kind of activated carbon supported type photochemical catalyst and Room Temperature Solid State self-propagating fast preparation method thereof, this catalyst that under the effect of little water soluble initiator prepared by greenization has oxidation resistance and reusable performance, is applicable to the wastewater treatments such as dyestuff, the light catalytic purifying of indoor pollution air and alkene epoxidation organic synthesis.
Background technology
China is over 30 years while economic maintenance rapid growth, and environment is subject to serious challenge.Blue mountains and green waters in the past fades away, and atmosphere pollution, river pollution, soil pollution serious threat the life of the people with healthy, and environmental pollution has become a large obstacle of restriction Economic Sustainable Development of China.China is the first big country of DYE PRODUCTION and consumption, dye well dyeing waste water has that the water yield is large, colourity is high, content of organics is high, the change of complex chemical composition, pH value greatly, the features such as bio-refractory are one of industrial wastewaters that difficulty of governance is larger.The processing method of industrial dye well dyeing waste water is more, generally adopts filtration, coagulation, is precipitated as main physical-chemical process (Coagulation Method, Fenton method, oxidizing process (Ozonation, O
3/ UV co-oxidation technology, O
3/ ultrasonic wave combination technique, Activated Carbon Catalytic Ozonation Process technology, metal oxide oxidation catalyst ozonation technology)), bioanalysis (aerobic method and anaerobic process) and coupling (homogeneous phase Fenton oxidation-Coagulation Method thereof, ultrasonic synergistic-ferrotianium bieletrolysis, coagulation-ABR(anaerobic baffled reactor, Anaerobic Baffled Reactor)/SBR(sequencing batch active sludge reactor, SequencingBatch Reactor)-activated sludge process group technology, coagulation-light electrolysis-bioanalysis, light electrolysis-ozone-bio combined method) etc. method etc.Be difficult to biodegradable aromatic series organic matter, heterocycle and polycyclic compound containing a large amount of in industrial wastewater, and content is higher complicated and changeable again, therefore the domestic and international process to this kind of waste water does not all have desirable processing method.Photocatalytic advanced oxidation technology degradation of dye waste water is the pollutant treatment technology that latest developments are got up.It utilizes ultraviolet light or visible light exposure to have the semiconductor light-catalyst (belonging to metal oxide semiconductor, sulfide or compound etc.) of photocatalytic activity, as titanium dioxide (TiO more
2), zinc oxide (ZnO), tungstic acid (WO
3), bismuth oxide (Bi
2o
3), cadmium sulfide (CdS), zinc sulphide (ZnS), WO
3/ TiO
2, p-n junction Cu
2o/BiVO
4, Ag
3pO
4/ BiVO
4etc..The principle of conductor photocatalysis is that semiconductor die intragranular has band structure, can band be usually full of the low energy valence band VB(Valent Band of electronics by one) and an empty higher energy conduction band CB(Conduct Band) form, separated by forbidden band between valence band and conduction band, the size in this region is called energy gap, it can differ from as band-gap energy Eg, and the band-gap energy of semiconductor is generally about 0.2 ~ 3.0eV; When semiconductor catalyst is penetrated in the illumination being more than or equal to band-gap energy with energy, the electronics e-on valence band VB is excited, and crosses forbidden band and enters conduction band CB, on valence band VB, meanwhile produce corresponding hole h
+, namely produce light induced electron/hole to (e
-/ h
+).Light induced electron on conduction band CB has stronger reducing power, and the photohole on valence band VB has very strong oxidisability.Move under electric field action or by the mode of diffusion, light induced electron/hole is to (e
-/ h
+) be adsorbed on material generation redox reaction on catalyst particle surface, or hole and electronics also may direct combinations on catalytic inner or surface, or captured by lattice surface defect.Generally can be described as under suitable illumination condition, completing of the photocatalytic process on semiconductor can be divided into four steps: be separated by the absorption electrons of light; Reactant is in the absorption of catalyst surface; The generation of interface oxidation reduction reaction; Product is at the desorption of catalyst surface.In light-catalyzed reaction, due to photohole and move to semiconductor surface and captured rear formation hydroxyl radical free radical by water or hydroxyl there is very strong oxidability, destroy C-C key, c h bond, C-N key, C-O key, O-H key and N-H key in organic matter, non-selectivity ground is oxidized most organic pollution (as all kinds of organic pollutions such as dyestuff, aldehydes matter, alkene, aldehydes, Polychlorinated biphenyls, surfactants) and makes it permineralization is nontoxic Small molecular CO
2and H
2o.
Current, the most popular semiconductor light-catalyst of industrial quarters and academia is TiO
2(being mainly Detitanium-ore-type and rutile-type).Titanium dioxide has the physical characteristics such as high specific area, high surface energy and blemish and the chemical property such as nontoxic, anti-light corrosivity is good, catalytic activity is high, reaction speed is fast, simultaneously high to the broad spectrum activity of organic pollutant degradation again, the thorough mineralizing and degrading of most organic pollutant can be made, the advantages such as less generation secondary pollution, are widely used in actual production life.TiO
2shortcoming be greater band gap (Eg ≈ 3.2eV), can only by the ultraviolet excitation of λ <387.5nm, and in the solar energy arriving ground, the energy of this wave band is still less than 5%, wherein actual effectively utilization is just less, thus significantly limit its investigation and application.According to artificial ultraviolet source, then need expensive equipment, and the recombination rate in light induced electron and hole is high, photo-quantum efficiency is very low.And visible ray accounts for 45% of solar energy, utilize visible ray as excitation source to TiO
2practical significant.Thus TiO is improved
2photochemical catalyst visible light-responded or develop meaning and the broad prospect of application that all kinds of visible light responsive photocatalyst has particular importance, and many new industries can be derived simultaneously.Main shows: 1) adopt semiconductors coupling to prepare the visible light catalyst of heterojunction structure; 2) work in coordination with doping effect by nonmetalloid and transition metal and prepare codope photochemical catalyst; 3) by nonmetalloid calking and displacement doped Ti O
2realize visible light catalytic effect, this method is considered to a key progress, but distinct issues are, the photochemical catalyst obtained activity is under visible light well below business-like Degussa P25 activity under ultraviolet light, and its light source used still has obvious ultraviolet light, particularly both activity are under ultraviolet light close; 4) dyestuff, complex sensitization TiO is utilized
2realize visible light catalytic effect; 5) novel visible catalyst is researched and developed; 6) loaded photocatalyst is researched and developed.As active carbon has flourishing pore structure, huge specific area and surperficial nonpolar chemical property, compound system can be formed with oxide, salt isoreactivity material, and catalytic activity research can be significantly improved show, can repeatedly recycle unlikely inactivation, be easy to be separated from liquid phase, solve the technical problems such as reacted separation difficulty better.This respect scientific research personnel and production working people have made a large amount of elaboration, and achieve main progress.
Cuprous oxide (Cu
2o) be the p-type semiconductor material of direct band gap, of many uses.The bactericide of marine antifouling priming paint is used as at coatings industry; Red glass and red enamel colouring agent is used in glass industry; Catalyst is used as in organic industry.Having utilizes cuprous oxide as the bibliographical information of photocatalyst for degrading organic dye waste water, also invention (the Fukumoto of copper compound matrix activated carbon deodorant is had, Kazuhiro et al, JP2004166920), activated charcoal carried copper oxide (CuO) is for the invention of the invention (CN1876232A) and a kind of activated carbon supported type photochemical catalyst and preparation method thereof (ZL201210024283.4) of coking chemical waste water.Although photocatalysis oxidation technique has good treatment effect to waste water from dyestuff, indoor pollution air etc., but this technique will realize industrialization also to be needed to answer catalyst activity component at selection visible ray, solve making a breakthrough property achievement in the separation of catalyst, the selection of carrier etc., particularly still needs further exploration in prepared by the greenization such as room temperature, solid phase reaction.
Summary of the invention
Technical problem to be solved by this invention is: the Room Temperature Solid State self-propagating simple method for preparing proposing a kind of dye wastewater treatment and indoor pollution air visible light response catalyst; the introducing of a small amount of water soluble starter had both solved solid state chemical reaction local medium and diffusion problem; also solve the stability protection problem of photochemical catalyst active principle, and carry out Treatment by Photocatalysis Oxidation with this shaped activated carbon such as powdery and particle loaded catalyst and have the process of waste water from dyestuff and indoor air pollutants and important organic synthesis.
Technical scheme of the present invention:
A kind of powder or granular active carbon load cuprous oxide photocatalyst, its component and content are:
Cuprous oxide weight percent content is 0.6-20%, and activated carbon weight degree is 80-99.4%.
A Room Temperature Solid State self-propagating fast preparation method for activated carbon-loaded cuprous oxide photocatalyst, the method comprises the following steps:
(1) active carbon is used 5mol/L H
2sO
4filter after soaking 12h, wash with water to neutral pH=7;
(2) active carbon that step (1) processed is put into baking oven, in 110 DEG C of oven dry, for subsequent use;
(3) active carbon taking a certain amount of step (2) surface modification, in reactor, adds CuSO successively by certain metering
45H
2o, NaOH, C
6h
12o
6(glucose) and Na
2sO
3and mix successively, the fully contact sodium sulfite of the relatively small amount (add the effect can played and regulate degree of oxidation and finished product purity);
CuSO
45H
2o, NaOH, C
6h
12o
6(glucose) and Na
2sO
3mass ratio be (2 ~ 6): (3 ~ 7): (0.5 ~ 1.2): (0.001 ~ 0.2); Be preferably 6:3:1:0.2;
(4) water-soluble poval (1%) solution of its weight 2% ~ 5% is added in the homogeneous solid mixture obtained in step (3) as the initiation protective agent in reaction; namely solve the required contact interface of local solid reaction, the diffusion problem of response matrix, also owing to producing polymer protection layer in solid-state diffusion reaction, dispersion and protection against oxidation problem are isolated to rising of cuprous oxide particle.Room temperature is placed, after several minutes, start initator region and near the product of the red nucleation of appearance, and carry out heat release, promote that liquid phase region fully contacts with solid phase interface, further diffusion reaction, continues to occur in the solid phase self-propagating reaction of reaction and diffusion between liquid-solid interface fast, load (deeply) red solid obtaining water content by redox reaction has the active carbon slurry of the cuprous oxide of class cube face pattern, is washed with water to neutrality;
(5) by loaded Cu that step (4) obtains
2the active carbon of O proceeds to dry 3h in the vacuum drying chamber of 80 DEG C, obtained activated carbon-loaded cuprous oxide photocatalyst.
Activated carbon-loaded cuprous oxide photocatalyst prepared by said method, its component and content are: cuprous oxide weight percent content is 0.6-20%, and activated carbon weight degree is 80-99.4%.
Described active carbon is column, cylindrical shape, amorphous granular shape or Powdered.
The beneficial effect that the present invention is compared to the prior art had:
The preparation of activated carbon-loaded cuprous oxide visible-light photocatalyst take copper sulphate as raw material, take active carbon as carrier, at room temperature with solid phase self-propagating reaction, cuprous oxide is downloaded on active carbon, method for preparing catalyst is easy, economy, good stability, photocatalytic activity be high.With the epoxidation organic synthesis of waste water, indoor aldehydes purification of air and the alkene such as this catalyst oxidation phenols, directly can carry out under ultraviolet-visible optical condition, be easy to operation, reaction condition is gentle, and the clearance of pollutant is high, selective good in organic synthesis.
Accompanying drawing explanation
Fig. 1 is activated carbon surface pattern.
Fig. 2 is the cubic Cu of activated carbon surface class prepared by embodiment 4
2o pattern.
Fig. 3 is Cu prepared by embodiment 4
2the energy dispersion spectrogram of O/AC.
Fig. 4 is Cu prepared by embodiment 4
2the photoelectron spectroscopy figure of O/AC.
Detailed description of the invention
Following embodiment further illustrates activated carbon-loaded cuprous oxide photocatalyst provided by the invention, preparation method and application.
Embodiment 1
Activated carbon-loaded cuprous oxide photocatalyst and preparation method
(1) by active carbon H
2sO
4(5mol/L) filter after soaking 12h, wash with water to neutral pH=7.
(2) active carbon that step (1) processed is put into baking oven, in 110 DEG C of oven dry, for subsequent use.
(3) take the pretreated active carbon of 3g, add 0.55gCuSO successively
45H
2o, 1.10gNaOH, 0.20g glucose and 0.04gNa
2sO
3, and mix successively, obtain pre-composition.
(4) add water-soluble protection initator (the 1% water-soluble poval solution) initiation reaction of about 2% in pre-composition step (3) obtained, after exothermic reaction completes, obtain the moistening loaded Cu of yellowish red color
2the activated charcoal solid of O, washing is to neutral.
(5) by loaded Cu that step (4) obtains
2the active carbon of O proceeds to dry 3h in the vacuum drying chamber of 80 DEG C, obtained load 3% cuprous oxide@active carbon (Cu
2o/AC) visible-light photocatalyst.
Embodiment 2
Step (1), (2) are identical with implementation method one;
(3) take the pretreated active carbon of 4g, add 1.20g CuSO successively
45H
2o, 2.40gNaOH, 0.42g glucose and 0.08g Na
2sO
3, and mix successively, obtain pre-composition.
(4) add water-soluble protection initator (the 1% water-soluble poval solution) initiation reaction of about 3% in pre-composition step (3) obtained, after exothermic reaction completes, obtain red moistening loaded Cu
2the activated charcoal solid of O, washing is to neutral.
(5) by loaded Cu that step (4) obtains
2the active carbon of O proceeds to dry 3h in the vacuum drying chamber of 80 DEG C, obtained load 6% cuprous oxide@active carbon (Cu2O/AC) visible-light photocatalyst.
Embodiment 3
Step (1), (2) are identical with implementation method one;
(3) take the pretreated active carbon of 5g, add 5.4g CuSO successively
45H
2o, 2.7gNaOH, 0.9g glucose and 0.18gNa
2sO
3, and mix successively, obtain pre-composition.
(4) add water-soluble protection initator (the 1% water-soluble poval solution) initiation reaction of about 4% in pre-composition step (3) obtained, after exothermic reaction completes, obtain red moistening loaded Cu
2the activated charcoal solid of O, washing is to neutral.
(5) by loaded Cu that step (4) obtains
2the active carbon of O proceeds to dry 3h in the vacuum drying chamber of 80 DEG C, obtained load 12% cuprous oxide@active carbon (Cu
2o/AC) visible-light photocatalyst.
Embodiment 4
Step (1), (2) are identical with implementation method one;
(3) take the pretreated active carbon of 3g, add 2.6g CuSO successively
45H
2o, 5.5gNaOH, 0.9g glucose and 0.2gNa
2sO
3, and mix successively, obtain pre-composition.
(4) add water-soluble protection initator (the 1% water-soluble poval solution) initiation reaction of about 5% in pre-composition step (3) obtained, after exothermic reaction completes, obtain red moistening loaded Cu
2the activated charcoal solid of O, washing is to neutral.
(5) by loaded Cu that step (4) obtains
2the active carbon of O proceeds to dry 3h in the vacuum drying chamber of 80 DEG C, obtained load 12% cuprous oxide@active carbon (Cu2O/AC) visible-light photocatalyst.
With the example of the waste water such as activated carbon-loaded cuprous oxide photocatalyst process phenols.
Example 5
Pipette methyl orange solution, the Cu prepared with example 4
2o/AC is photochemical catalyst, utilizes the photochemical reactor that Kaifeng Red Star scientific instrument factory produces, and employing dominant wavelength is that the 300W mercury lamp of 365nm does radiation source, take 463nm as the maximum absorption wavelength of methyl orange solution, surveys its absorbance.The photocatalytic activity η=(A of sample
0-A
t)/A
0× 100%.After degraded 2h, degradation rate reaches more than 92%.Catalyst after recovery can use more than 3 times, and degradation efficiency still reaches 90%.
Example 6
Get the olefin solution (styrene) of certain volume, add the Cu prepared with example 4
2o/AC is photochemical catalyst, add oxidants hydrogen peroxide, under organic solvent effect, utilize the photochemical reactor that Kaifeng Red Star scientific instrument factory produces, adopt dominant wavelength to be that the 300W mercury lamp of 365nm does radiation source, reaction terminates the rear Styryl oxide utilizing gas chromatographic detection to produce, and it is selective reaches more than 46%, and catalyst uses more than 3 times, the selective of product still reaches 45%.
The degradation rate of being degraded from example 5, the Be very effective of activated carbon-loaded cuprous oxide catalyze and degrade organic pollutants.Selective from example 6 product, the Be very effective of activated carbon-loaded cuprous oxide catalyzed alkene epoxy reaction organic synthesis.The preparation method of the activated carbon-loaded cuprous oxide photocatalyst that the present invention obtains is simple, cheap, good stability, high to the clearance of organic pollution (comprising indoor aldehydes etc.), and be applied on high selectivity alkene epoxidation organic synthesis, reusable, there is good economic competitiveness.
Claims (2)
1. the preparation method of a powder or granular active carbon load cuprous oxide photocatalyst, by Room Temperature Solid State self-propagating reaction, cuprous oxide is deposited on the active carbon of acid surfaces modification, the component of described catalyst and content are: cuprous oxide weight percent content is 0.6-20%, and activated carbon weight degree is 80-99.4%; The method comprises the following steps:
(1) active carbon is used 5mol/L H
2sO
4filter after soaking 12h, wash with water to neutral pH=7;
(2) active carbon that step (1) processed is put into baking oven, in 110 DEG C of oven dry, for subsequent use;
(3) by the active carbon of step (2) surface modification in reactor, add CuSO successively
45H
2o, NaOH, C
6h
12o
6and Na
2sO
3and mix, fully contact;
(4) the water-soluble poval solution of its weight 2% ~ 5% is added in the homogeneous solid mixture obtained in step (3) as the initiation protective agent in reaction, the mass percent concentration of described poly-vinyl alcohol solution is 1%, room temperature is placed, there is solid phase self-propagating reaction, obtained the active carbon slurry of cuprous oxide by redox reaction, be washed with water to neutrality;
(5) by loaded Cu that step (4) obtains
2the active carbon of O proceeds to dry 3h in the vacuum drying chamber of 80 DEG C, obtained activated carbon-loaded cuprous oxide photocatalyst.
2. the purposes of activated carbon-loaded cuprous oxide photocatalyst prepared of the method for claim 1, is characterized in that: this catalyst is used as organic dyestuff, the photocatalytic degradation of aldehydes and the organic synthesis of photocatalysis alkene epoxidation.
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| CN104014341B (en) * | 2014-06-12 | 2015-12-30 | 淮北师范大学 | A kind of Interface Reduction legal system is for Cu 2o/Ca (OH) 2the method of nano composite photo-catalyst |
| CN104310504B (en) * | 2014-09-30 | 2016-03-02 | 渤海大学 | The treatment process of organic pollutant in a kind of dyeing waste water |
| CN107233898A (en) * | 2017-07-10 | 2017-10-10 | 苏州科技大学 | Preconcentration with activated carbon collaboration full spectrum light catalysis material and preparation method thereof |
| CN108325527B (en) * | 2018-03-27 | 2021-01-05 | 昆明理工大学 | Cu2Preparation method and application of O-AC photocatalyst |
| CN108771964B (en) * | 2018-06-21 | 2021-06-22 | 江苏大学 | Nano cuprous oxide micro-electrolysis deodorization device |
| CN109222210B (en) * | 2018-08-13 | 2020-07-17 | 云南中烟工业有限责任公司 | Modified carbon material, preparation method and application thereof |
| CN110787818B (en) * | 2019-09-05 | 2022-04-15 | 宁夏大学 | Propylene epoxidation catalyst, preparation method and application thereof |
| CN112717636B (en) * | 2019-10-28 | 2023-05-26 | 中国石油化工股份有限公司 | Treatment device and method for refinery VOCs waste gas |
| CN112723492B (en) * | 2020-12-18 | 2023-05-26 | 广州市铁鑫金属结构有限公司 | Preparation method and application of cuprous oxide-loaded activated carbon |
| CN112916006B (en) * | 2021-02-01 | 2023-04-11 | 中国科学院合肥物质科学研究院 | Preparation method and application of irregular carbon-coated copper oxide catalyst |
| US11872547B2 (en) * | 2021-03-31 | 2024-01-16 | Council Of Scientific & Industrial Research | Process for the photocatalytic allylic oxidation of olefins using carbon dioxide |
| CN113479988B (en) * | 2021-08-16 | 2022-09-13 | 南京工业大学 | Visible light catalysis-Fenton membrane reactor for wastewater treatment |
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| TW200843840A (en) * | 2007-05-09 | 2008-11-16 | Pao-Chu Liu | Catalysts for treating acid and halogen gases and production methods thereof |
| CN102259017A (en) * | 2010-05-31 | 2011-11-30 | 上海图和环保材料科技有限公司 | Novel composite nano visible light catalyst and preparation method thereof |
| CN102580742B (en) * | 2012-02-05 | 2013-07-31 | 淮北师范大学 | Activated carbon-loaded cuprous oxide photocatalyst and preparation method thereof |
| CN103240089B (en) * | 2013-05-21 | 2014-10-08 | 淮北师范大学 | Solid-phase mechanical-chemical preparation method of nano Cu2O photocatalyst |
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