CN103641231A - Application of cupric borate as visible light catalyst for degrading dye wastewater - Google Patents

Application of cupric borate as visible light catalyst for degrading dye wastewater Download PDF

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CN103641231A
CN103641231A CN201310661010.5A CN201310661010A CN103641231A CN 103641231 A CN103641231 A CN 103641231A CN 201310661010 A CN201310661010 A CN 201310661010A CN 103641231 A CN103641231 A CN 103641231A
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visible light
methylene blue
borate
water
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CN103641231B (en
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陈爱民
邵晨熠
薄盈盈
胡军
汪晶
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Zhejiang University of Technology ZJUT
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses the application of cupric borate Cu3B2O6 as a visible light catalyst. Specifically, cupric borate can be used as a visible light catalyst for degrading organic dye wastewater under the condition of visible light, and especially can be used for carrying out visible light catalytic degradation on dye wastewater containing methylene blue. The invention also discloses a specific application method. According to the invention, provided Cu3B2O6 powder is added into a methylene blue solution, then a photocatalytic degradation reaction is performed under the condition of visible light (wavelength: 420-800 nm), and the removal ratio of methylene blue in water is as high as 99.52%, therefore, cupric borate Cu3B2O6 is high in photocatalytic degradation ability, and advantageous to the industrialization of a Cu3B2O6 photocatalytic dye wastewater treatment technology.

Description

A kind of application of visible light catalyst copper borate degradation of dye waste water
(1) technical field
The present invention relates to a kind of novel visible catalyst copper borate for the photocatalysis treatment of waste water from dyestuff, belong to the photocatalysis technology in environmental improvement.
(2) background technology
Enter 21 century, along with the raising of industrialization degree, problem of environmental pollution is day by day serious, and wherein the processing of waste water from dyestuff is particularly thorny.In waste water from dyestuff, conventionally contain the organic pollutant of some high toxicity difficult degradations, because its Pollutant levels are high, complicated component, biodegradability be poor, adopt ordinary method to be difficult to it effectively to process, therefore the mankind's health and species diversity have been caused to huge threat.
Photochemical catalysis, as a kind of deep oxidation method, has been acknowledged as pollutant removal technology most with prospects.But through more than 30 years, study extensively and profoundly, photocatalysis technology is still difficult to realization and efficiently transforms at an easy rate and utilize sun power.Major cause is that a series of wide band gap semiconducter photocatalysts of developing of people are as NaTaO 3, TiO 2deng, only in ultraviolet light range, have response, and the UV-light part not enough sunlight total energy of wavelength below 400nm 5%, solar energy mainly concentrates on the visible-range of 400～700nm, reaches 43% of total energy.Therefore developing visible light-responded catalyzer is to improve solar energy utilization ratio, finally realizes the key of photocatalysis technology commercial application.
Cu 3b 2o 6it is a kind of borate material with middle Gap States, as a kind of intrinsic p-TCOs, without doping, just there is the middle energy gap between conduction band and valence band, and do not have lattice defect, therefore under visible ray, just having stronger photo-catalysis capability, is a kind of novel visible light catalyst.Yet at present about the research report of copper borate few, and mostly concentrate on magnetic research above, about the research of its photocatalytic degradation of dye, not yet see report.To the multiplex high temperature solid-state method of the preparation method of copper borate, Petrakovskii etc. (Physics of the Solid State, Vol.41,610-612) are with Li at present 2o-CuO-B 2o 3system is prepared monocrystalline Cu with solid sintering technology 3b 2o 6, temperature of reaction is 1200 ℃.But owing to there being the problems such as energy consumption is higher, products therefrom local organization is inhomogeneous, purity is lower, therefore in industrial production, be not widely used.
(3) summary of the invention
The problem to be solved in the present invention is: overcome current traditional photochemical catalysis reagent (as TiO 2) energy gap is large, to problems such as visible ray utilization ratio are low, provides a kind of novel visible catalyst copper borate (Cu 3b 2o 6), for visible light photocatalytic degradation organic dye, particularly to methylene blue.In addition, the present invention replaces high temperature solid-state method to prepare the Cu of single crystal structure by sol-gel method 3b 2o 6, this method is simple, equipment is simple, synthesis condition is gentle, have industrialization future.
The technical scheme that the present invention takes the problem that will solve is:
Copper borate Cu 3b 2o 6application is as visible light catalyst.Concrete, copper borate can be used as visible light catalyst catalyzed degradation organic dye waste water under visible ray.Further, described visible light catalyst copper borate is particularly useful for the visible light photocatalytic degradation to the waste water from dyestuff containing methylene blue.
Concrete, the method for described application is:
5～50mg/L adds visible light catalyst copper borate Cu containing in the waste water from dyestuff of methylene blue 3b 2o 6the quality that adds of copper borate is counted preferably 0.8～1.2mg/mL of 0.6～1.5mg/mL(with the volume of waste water from dyestuff), under light source within the scope of wavelength 420～800nm irradiates, stirring reaction under room temperature, light-catalyzed reaction time 1～6h(is 3～6h preferably), remove by filter catalyzer, obtain degraded and remove the water body after methylene blue.
In application method of the present invention, described visible light catalyst copper borate preferably makes by the following method:
Water-soluble mantoquita, whipping agent are mixed than the ratio of 1:0.1～6 in amount of substance, add the aqueous solution that water is made into cupric, at room temperature stir preferably 2～3h of 1～4h(), in solution, drip 0.05～2.0mol/L boric acid or tributyl borate solution again, in the amount of substance that makes boron in the boric acid that adds or tributyl borate solution and solution, the ratio of the amount of substance of copper is 0.6～2:1, at room temperature stir preferably 2～3h of 1～4h(), then at 120～170 ℃ of temperature, (preferably at 140～150 ℃ of temperature) dry, and obtain brown xerogel; Xerogel is calcined preferably 6～10h of 2～10h(in 550～1000 ℃ (preferably 850～900 ℃) under air atmosphere), obtain cyan meal; The deionized water wash of 0.1～1.0mol/L hydrochloric acid or heat for described meal, centrifugal, powder is dry at 40～120 ℃ (preferably 80～100 ℃), makes visible light catalyst copper borate Cu 3b 2o 6.
Described water-soluble mantoquita is preferably cupric nitrate, neutralized verdigris or copper sulfate.
Described whipping agent is preferably glucose, sucrose, oxysuccinic acid or tartrate.
In the aqueous solution of described cupric, wherein the concentration of cupric ion is preferably 0.05～0.15mol/L.
The deionized water wash of 0.1～1.0mol/L hydrochloric acid or heat for described meal is generally with the deionized water wash meal of 0.1～1.0mol/L hydrochloric acid or 60～100 ℃ 3～4 times.
In described method, the ratio of the amount of substance of preferably water dissolubility mantoquita, whipping agent is 1:2～3, most preferably 1:2.
Preferably in copper, boric acid or the tributyl borate solution in described water-soluble mantoquita, the ratio of the amount of substance of boron is preferably 1:0.7～1.3, more preferably 1:1.
Remarkable advantage of the present invention is:
1. first by Cu 3b 2o 6be applied to the photocatalysis field of waste water from dyestuff, efficient degradation dyestuff under visible ray, can realize the making full use of of clean energy sun power, and is a kind of novel visible light catalyst.
2. preparation method is simple, easily realizes suitability for industrialized production.
Product of the present invention be uniformly dispersed, sheet or bar-shaped Cu 3b 2o 6monocrystalline, and under visible ray, waste water from dyestuff is had to stronger photodegradation ability, to the clearance of water Methylene Blue up to 99.52%.Be conducive to Cu 3b 2o 6the industrialization of photocatalysis treatment waste water from dyestuff technology.
The synthetic copper borate of sol-gel method for the present invention, and use it for methylene blue photocatalytic degradation can have been obtained to novel visible light catalyst, the dye wastewater treatment technology for exploitation with development prospect provides Research Thinking and theoretical support.
(4) accompanying drawing explanation
The Cu of the single crystal structure that Fig. 1 embodiment 1 makes 3b 2o 6xRD figure.
The Cu of the single crystal structure that Fig. 2 embodiment 1 makes 3b 2o 6sEM figure.
The Cu of the single crystal structure that Fig. 3 embodiment 2 makes 3b 2o 6tEM figure.
The Cu of the single crystal structure that Fig. 4 embodiment 2 makes 3b 2o 6uV-Vis DRS figure.
The Cu of Fig. 5 single crystal structure 3b 2o 6as photocatalytic degradation methylene blue, the change in concentration figure of methylene blue, in figure, curve a is the degraded situation of embodiment 10 Methylene Blues, and curve b is the photodegradation situation of embodiment 11 Methylene Blues, and curve c is the photodegradation situation of example 12 Methylene Blues.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this.
Light source in the embodiment of the present invention is the 500W xenon lamp that is placed in two glass jacket (logical water of condensation), and adopts edge filter to obtain respectively the visible ray of 420～800nm.
Embodiment 1
Take respectively 2.5mmol(0.5g) neutralized verdigris (Cu (CH 3cOO) 2h 2o), 7.5mmol glucose (1.35g) is dissolved in 20mL distilled water, magnetic agitation 2h.By 2.5mmol(1.55g) boric acid is dissolved in 30mL deionized water, then boric acid aqueous solution is added in previous reaction liquid to magnetic agitation 2h.Then by mixed solution in 150 ℃ of oven dry of baking oven, obtain brown xerogel, xerogel is placed in to roasting 6h at 850 ℃, obtain blackish green powder, use respectively the deionized water wash 3～4 times of 0.1mol/L hydrochloric acid and 60 ℃, centrifugal, powder is the dry Cu that obtains at 60 ℃ 3b 2o 6monocrystalline 0.21g.Through XRD, detect, as shown in Figure 1, gained Cu 3b 2o 6for pure substance, corresponding PDF card number: 28-398; Through SEM, detect, as shown in Figure 2, sample Cu 3b 2o 6for Rod-like shape, the diameter of rod is about 300～600nm, and length is about 6 μ m left and right.
Get 50mg Cu obtained above 3b 2o 6powder adds the methylene blue solution (50mg/L) of 45mL, be placed in BL-GHX-V photochemical reaction instrument, open light source, under 420nm light source, 25 ℃, 1200rpm condition, react, reactor took out 5mL reaction solution every 1 hour, with disposable aspiration needle strainer filtration catalizer, gained solution is measured dye strength with Shimadzu 2550 type spectrophotometry instrument, under 664nm, measure the absorbancy of waste water from dyestuff, calculate the concentration of methylene blue.The method reaction 6h reaches 97.67% to the clearance of water Methylene Blue.
Embodiment 2
Take respectively the cupric nitrate (Cu (NO of 2.5mmol 3) 23H 2o), 5.0mmol oxysuccinic acid is dissolved in 20mL distilled water, magnetic agitation 3h.2.5mmol boric acid is dissolved in 30mL deionized water, then this drop is added in previous reaction liquid to magnetic agitation 4h.Then by mixed solution in 140 ℃ of oven dry of baking oven, obtain brown gel, gel is placed in to roasting 7h at 900 ℃, obtain blackish green powder, use respectively the deionized water wash 3～4 times of 0.21mol/L hydrochloric acid and 80 ℃, centrifugal, powder is the dry Cu that obtains at 80 ℃ 3b 2o 6sample.Through XRD, detect, result is with accompanying drawing 1, gained Cu 3b 2o 6for pure substance, corresponding PDF card number: 28-398; Through HRTEM test, as shown in Figure 3, show the Cu of preparation 3b 2o 6for single crystal structure.Through UV-vis test, UV-Vis DRS figure as shown in Figure 4, the Cu that as calculated prepared by gained 3b 2o 6energy gap is 2.34eV, and the width of top of valence band and mid-gap is 1.78eV.
Get 45mg Cu obtained above 3b 2o 6powder adds 50mL methylene blue solution (45mg/L), under the visible ray of 500nm, 25 ℃, 1200rpm condition, reacts, and timing sampling is also determined the concentration of methylene blue.The method reaction 5h reaches 89.33% to the clearance of water Methylene Blue.
Embodiment 3
Take respectively the cupric nitrate (Cu (NO of 2.5mmol 3) 23H 2o), 7.5mmol glucose is dissolved in 20mL distilled water, magnetic agitation 3h.1.75mmol boric acid is dissolved in 30mL deionized water, then this drop is added in previous reaction liquid to magnetic agitation 2h.Then by mixed solution in 120 ℃ of oven dry of baking oven, obtain brown gel, gel is placed in to roasting 7h at 850 ℃, obtain blackish green powder, use respectively the deionized water wash 3～4 times of 0.4mol/L hydrochloric acid and 80 ℃, centrifugal, powder is the dry Cu that obtains at 60 ℃ 3b 2o 6 sample.As embodiment 1, gained Cu 3b 2o 6for pure substance, and it is single crystal structure.
Get 40mg Cu obtained above 3b 2o 6powder adds 35mL methylene blue solution (35mg/L), under the visible ray of 600nm, 25 ℃, 1200rpm condition, reacts, and timing sampling is also determined the concentration of methylene blue.The method reaction 5h reaches 86.48% to the clearance of water Methylene Blue.
Embodiment 4
Take respectively the neutralized verdigris (Cu (CH of 2.5mmol 3cOO) 2h 2o), 7.5mmol sucrose is dissolved in 20mL distilled water, magnetic agitation 2h.3.25mmol tributyl borate is dissolved in 30mL deionized water, then this drop is added in previous reaction liquid to magnetic agitation 2h.Then by mixed solution in 170 ℃ of oven dry of baking oven, obtain brown gel, gel is placed in to roasting 10h at 600 ℃, obtain blackish green powder, use respectively the deionized water wash 3～4 times of 0.6mol/L hydrochloric acid and 80 ℃, centrifugal, powder is the dry Cu that obtains at 80 ℃ 3b 2o 6 sample.As embodiment 1, gained Cu 3b 2o 6for pure substance, and it is single crystal structure.
Get 30mg Cu obtained above 3b 2o 6powder adds 45mL methylene blue solution (30mg/L), under the visible ray of 640nm, 25 ℃, 1200rpm condition, reacts, and timing sampling is determined the concentration of methylene blue.The method reaction 4h reaches 79.59% to the clearance of water Methylene Blue.
Embodiment 5
Take respectively the neutralized verdigris (Cu (CH of 2.5mmol 3cOO) 2h 2o), 15mmol sucrose is dissolved in 20mL distilled water, magnetic agitation 2h.4.0mmol boric acid is dissolved in 30mL deionized water, then this drop is added in previous reaction liquid to magnetic agitation 2h.Then by mixed solution in 150 ℃ of oven dry of baking oven, obtain brown gel, gel is placed in to roasting 10h at 550 ℃, obtain blackish green powder, use respectively the deionized water wash 3～4 times of 1.0mol/L hydrochloric acid and 80 ℃, centrifugal, powder is the dry Cu that obtains at 100 ℃ 3b 2o 6 sample.As embodiment 1, gained Cu 3b 2o 6for pure substance, and it is single crystal structure.
Get 40mg Cu obtained above 3b 2o 6powder adds 50mL methylene blue solution (25mg/L), under the visible ray of 700nm, 25 ℃, 1200rpm condition, reacts, and timing sampling is also determined the concentration of methylene blue.The method reaction 4h reaches 76.49% to the clearance of water Methylene Blue.
Embodiment 6
Take respectively the copper sulfate (CuSO of 2.5mmol 45H 2o), 10mmol glucose is dissolved in 20mL distilled water, magnetic agitation 2h.2.5mmol tributyl borate is dissolved in 30mL deionized water, then this drop is added in previous reaction liquid to magnetic agitation 2h.Then by mixed solution in 130 ℃ of oven dry of baking oven, obtain brown gel, gel is placed in to roasting 10h at 550 ℃, obtain blackish green powder, use respectively the deionized water wash 3～4 times of 0.9mol/L hydrochloric acid and 70 ℃, centrifugal, powder is the dry Cu that obtains at 70 ℃ 3b 2o 6 sample.As embodiment 1, gained Cu 3b 2o 6for pure substance, and it is single crystal structure.
Get 30mg Cu obtained above 3b 2o 6powder adds 35mL methylene blue solution (40mg/L), under the visible ray of 750nm, 25 ℃, 1200rpm condition, reacts, and timing sampling is also determined the concentration of methylene blue.The method reaction 3h reaches 76.83% to the clearance of water Methylene Blue.
Embodiment 7
Take respectively the neutralized verdigris (Cu (CH of 2.5mmol 3cOO) 2h 2o), 0.25mmol oxysuccinic acid is dissolved in 20mL distilled water, magnetic agitation 2h.2.5mmol tributyl borate is dissolved in 30mL deionized water, then this drop is added in previous reaction liquid to magnetic agitation 2h.Then by mixed solution in 170 ℃ of oven dry of baking oven, obtain brown gel, gel is placed in to roasting 9h at 650 ℃, obtain blackish green powder, use respectively the deionized water wash 3～4 times of 0.1mol/L hydrochloric acid and 70 ℃, centrifugal, powder is the dry Cu that obtains at 80 ℃ 3b 2o 6 sample.As embodiment 1, gained Cu 3b 2o 6for pure substance, and it is single crystal structure.
Get 30mg Cu obtained above 3b 2o 6powder adds 50mL methylene blue solution (15mg/L), under the visible ray of 720nm, 25 ℃, 1200rpm condition, reacts, and timing sampling is also determined the concentration of methylene blue.The method reaction 3h reaches 86.78% to the clearance of water Methylene Blue.
Embodiment 8
Take respectively the neutralized verdigris (Cu (CH of 2.5mmol 3cOO) 2h 2o), 5.0mmol tartrate is dissolved in 20mL distilled water, magnetic agitation 2h.2.5mmol boric acid is dissolved in 30mL deionized water, then this drop is added in previous reaction liquid to magnetic agitation 2h.Then by mixed solution in 170 ℃ of oven dry of baking oven, obtain brown gel, gel is placed in to roasting 6h at 750 ℃, obtain blackish green powder, use respectively the deionized water wash 3～4 times of 0.16mol/L hydrochloric acid and 70 ℃, centrifugal, powder is the dry Cu that obtains at 100 ℃ 3b 2o 6 sample.As embodiment 1, gained Cu 3b 2o 6for pure substance, and it is single crystal structure.
Get 35mg Cu obtained above 3b 2o 6powder adds 50mL methylene blue solution (20mg/L), under the visible ray of 540nm, 25 ℃, 1200rpm condition, reacts, and timing sampling is also determined the concentration of methylene blue.The method reaction 6h reaches 96.42% to the clearance of water Methylene Blue.
Embodiment 9
Take respectively the copper sulfate (CuSO of 2.5mmol 45H 2o), 5.0mmol tartrate is dissolved in 20mL distilled water, magnetic agitation 2h.2.5mmol boric acid is dissolved in 30mL deionized water, then this drop is added in previous reaction liquid to magnetic agitation 2h.Then by mixed solution in 150 ℃ of oven dry of baking oven, obtain brown gel, gel is placed in to roasting 2h at 850 ℃, obtain blackish green powder, use respectively the deionized water wash 3～4 times of 0.1mol/L hydrochloric acid and 70 ℃, centrifugal, powder is the dry Cu that obtains at 60 ℃ 3b 2o 6 sample.As embodiment 1, gained Cu 3b 2o 6for pure substance, and it is single crystal structure.
Get 45mg Cu obtained above 3b 2o 6powder adds 50mL methylene blue solution (30mg/L), under the visible ray of 450nm, 25 ℃, 1200rpm condition, reacts, and timing sampling is also determined the concentration of methylene blue.The method reaction 6h reaches 87.88% to the clearance of water Methylene Blue.
Embodiment 10
50mL methylene blue solution (50mg/L) is placed in to photoreactor, under the visible ray of 500nm, 25 ℃, 1200rpm condition, reacts, timing sampling is also determined the concentration of methylene blue.The method reaction 6h is only 11% to the clearance of water Methylene Blue.Under different sample times, the change curve of sampling concentration/methylene blue initial concentration of methylene blue is as accompanying drawing 5 curve a.
Embodiment 11
Get the Cu that 45mg embodiment 1 makes 3b 2o 6powder, adds 25mL methylene blue solution (50mg/L).Mixed system is placed in to photoreactor: under 25 ℃, 1200rpm, dark condition, react, timing sampling is also determined the concentration of methylene blue.The method reaction 6h is only 26.58% to the clearance of water Methylene Blue.Under different sample times, the change curve of sampling concentration/methylene blue initial concentration of methylene blue is as accompanying drawing 5 curve b.
Embodiment 12
Get the Cu that 50mg embodiment 1 makes 3b 2o 6powder, adds 25mL methylene blue solution (50mg/L), under the visible ray of 620nm, 25 ℃, 1200rpm condition, reacts, and timing sampling is also determined the concentration of methylene blue.The method 6h reaches 99.52% to the clearance of water Methylene Blue.Under different sample times, the change curve of sampling concentration/methylene blue initial concentration of methylene blue is as accompanying drawing 5 curve c.

Claims (7)

1. copper borate Cu 3b 2o 6application as visible light catalyst.
2. application as claimed in claim 1, is characterized in that copper borate is as the application of visible light catalyst catalyzed degradation organic dye waste water under visible ray.
3. application as claimed in claim 2, is characterized in that copper borate contains the application of the waste water from dyestuff of methylene blue as visible light catalyst catalyzed degradation under visible ray.
4. application as claimed in claim 3, is characterized in that the method for described application is: 5～50mg/L adds visible light catalyst copper borate Cu containing in the waste water from dyestuff of methylene blue 3b 2o 6, the quality that adds of copper borate is counted 0.6～1.5mg/mL with the volume of waste water from dyestuff, under the light source within the scope of wavelength 420～800nm irradiates, stirring reaction under room temperature, light-catalyzed reaction time 1～6h, removes by filter catalyzer, obtains degraded and removes the water body after methylene blue.
5. application as claimed in claim 4, is characterized in that the quality that adds of described copper borate is counted 0.8～1.2mg/mL with the volume of waste water from dyestuff.
6. application as claimed in claim 4, is characterized in that the light-catalyzed reaction time is 3～6h.
7. application as claimed in claim 4, it is characterized in that described visible light catalyst copper borate makes by the following method: by water-soluble mantoquita, whipping agent mixes than the ratio of 1:0.1～6 in amount of substance, add the aqueous solution that water is made into cupric, at room temperature stir 1～4h, in solution, drip 0.05～2.0mol/L boric acid or tributyl borate solution again, in the amount of substance that makes boron in the boric acid that adds or tributyl borate solution and solution, the ratio of the amount of substance of copper is 0.6～2:1, at room temperature stir 1～4h, then at 120～170 ℃ of temperature, dry, obtain xerogel, xerogel in 550～1000 ℃ of calcining 2～10h, obtains meal under air atmosphere, for described meal, the deionized water wash of 0.1～1.0mol/L hydrochloric acid or heat, centrifugal, and gained powder is dried at 40～120 ℃, makes bar-like single crystal structure copper borate Cu 3b 2o 6, described water-soluble mantoquita is cupric nitrate, neutralized verdigris or copper sulfate, described whipping agent is glucose, sucrose, oxysuccinic acid or tartrate.
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CN104492419A (en) * 2014-12-28 2015-04-08 桂林理工大学 Visible light responding photocatalyst LiBi3B3O11 and preparation method thereof
CN104525208A (en) * 2014-12-28 2015-04-22 桂林理工大学 Photocatalyst LiFe2B3O8 with visible light response and preparation method thereof
CN104645992A (en) * 2014-11-30 2015-05-27 桂林理工大学 Photocatalyst Li3Cu2BO5 with visible-light response and preparation method thereof
CN105399108A (en) * 2015-12-21 2016-03-16 浙江工业大学 Preparation method of visible-light response Cu3B2O6 with mesoporous structure
CN105879896A (en) * 2016-05-12 2016-08-24 湖南农业大学 Preparation method of Cu3B2O6/g-C3N4 (cupric borate/graphitic carbon nitride) heterojunction photocatalyst and method for degrading methylene blue dye wastewater
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CN109850987A (en) * 2019-01-29 2019-06-07 闽江学院 Utilize the method for lanthanum manganate catalysis II waste water of ultrasonic degradation organic dyestuff gold orange
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CN104645992A (en) * 2014-11-30 2015-05-27 桂林理工大学 Photocatalyst Li3Cu2BO5 with visible-light response and preparation method thereof
CN104437505A (en) * 2014-12-28 2015-03-25 桂林理工大学 Visible light responded photocatalyst LiFeB2O5 and preparation method thereof
CN104492419A (en) * 2014-12-28 2015-04-08 桂林理工大学 Visible light responding photocatalyst LiBi3B3O11 and preparation method thereof
CN104525208A (en) * 2014-12-28 2015-04-22 桂林理工大学 Photocatalyst LiFe2B3O8 with visible light response and preparation method thereof
CN105399108A (en) * 2015-12-21 2016-03-16 浙江工业大学 Preparation method of visible-light response Cu3B2O6 with mesoporous structure
CN105879896A (en) * 2016-05-12 2016-08-24 湖南农业大学 Preparation method of Cu3B2O6/g-C3N4 (cupric borate/graphitic carbon nitride) heterojunction photocatalyst and method for degrading methylene blue dye wastewater
CN105879896B (en) * 2016-05-12 2018-03-06 湖南农业大学 Cu3B2O6/g‑C3N4The preparation method of heterojunction photocatalyst and its method for degradation of methylene blue waste water from dyestuff
CN108455700A (en) * 2018-02-07 2018-08-28 长兴科创科技咨询有限公司 A kind of method of photocatalytic treatment of industrial waste water
CN109850987A (en) * 2019-01-29 2019-06-07 闽江学院 Utilize the method for lanthanum manganate catalysis II waste water of ultrasonic degradation organic dyestuff gold orange
CN109850987B (en) * 2019-01-29 2022-03-08 闽江学院 Method for degrading organic dye golden orange II wastewater by using lanthanum manganate as catalyst and ultrasonic waves
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