CN103769050A - Electrochemical method for preparing activated carbon fibers with photocatalysis function - Google Patents

Abstract

The invention discloses a preparation method for activated carbon fibers with a photocatalysis function. The activated carbon fibers for immobilizing graphite phase carbon nitride are prepared by an electrochemical deposition method by taking activated carbon fibers, dicyanodiamine, N,N-dimethylformamide and the like as main raw materials. The activated carbon fibers have an adsorption function and the photocatalysis function. Under a condition of darkness or insufficient light, pollutants can be purified under the adsorption function of the activated carbon fibers; under a condition of sufficient light, the pollutants can be purified under the adsorption function and the photocatalysis function; in-situ regeneration of the adsorption function of the activated carbon fibers can be realized; labor, resource and financial consumption of a regeneration process is greatly reduced. Successful research on the activated carbon fibers has an important significance for relieving of insufficience of activated carbon fiber supply in China.

Description

Electrochemical production photo-catalysis function NACF

Technical field

The invention belongs to NACF preparation field, be specifically related to a kind ofly there is light and urge the preparation method of functional activity charcoal fiber.

Background technology

The advantages such as its pore structure prosperity of active carbon fibre denapon, absorption affinity is strong, surface functional group is abundant, chemical inertness, are widely used in the fields such as gas absorption purification, polluted-water improvement, drink water purifying and food industry, chemical industry.But because NACF kind is few, with low content of technology, lack functionalization high-quality special activated carbon fiber, the higher level application of marching toward of restriction China NACF industry.By NACF modification, develop can carry out efficiently pollutant, the functional activity charcoal fiber of deep purifying, being the use cost that reduces NACF, expanding its scope of application, improving the effective way of its utilization ratio, is the direction of NACF industry future development.

Due to NACF to the absorption of pollutant mainly take micropore filling as main, adsorbance is limited, in short time, can reach absorption saturated and lose adsorption capacity, adsorbing saturated NACF becomes secondary pollution source, must can again utilize its processing of regenerate.NACF renovation process can be divided into two classes generally at present: the one, manage to make adsorbate desorption, by creating the condition corresponding with underload (introduce material or energy and make reaction force attenuation or the disappearance between adsorption molecule and NACF), remove adsorbate; The 2nd, rely on thermal decomposition or redox reaction to destroy the structure of adsorbate, remove adsorbate.Traditional renovation process mainly contains heat regeneration, chemicals regeneration, solvent reclamation, bio-regeneration etc., but due to its exist efficiency low, expend the defects such as height, operating condition harshness, complex process, conventional regeneration method can not meet the demand of present industrial development.Therefore study a kind of renovation process at normal temperature, normal pressure, low cost, high efficiency, operating procedure Dan Jian and become the focus of domestic and international research.

Summary of the invention

The object of the present invention is to provide and a kind ofly there is light and urge the preparation method of functional activity charcoal fiber.The photo-catalysis function NACF that the present invention makes has photo-catalysis function and adsorption function, and NACF can in-situ regeneration under illumination.

For achieving the above object, the present invention adopts following technical scheme:

The NACF that adopts the immobilized graphite-phase carbonitride of electrochemical production, comprises the following steps:

(1) will there is the NACF that electric conductivity and resistivity are less than 80k Ω/m, and boil after cleaning with the hydrochloric acid of 2wt.%, then be washed with distilled water to neutrality, in baking oven, dry 24h;

(2) the DMF solution that the NACF of step (1) is placed in to dicyanodiamine soaks 24h;

(3) process of immobilized graphite-phase carbonitride is carried out in electrolytic cell, electrochemical deposition condition: with the N of dicyanodiamine, N dimethyl formamide solution is as electrolyte, take graphite as anode, take the NACF of step (2) as negative electrode, power supply is dc source, electrolytic process voltage 500 ~ 2000V, 25 ~ 30 ℃ of temperature, time 1 ~ 5h;

(4) from electrolytic cell, take out the NACF of negative electrode, fully wash, dry with distilled water, make the NACF of immobilized graphite-phase carbonitride.

In the DMF solution of described dicyanodiamine, the concentration of dicyanodiamine is 0.05 ~ 0.15mol/L.

Remarkable advantage of the present invention is: the NACF that the present invention makes not only has adsorption function, and has photo-catalysis function.It relies on the adsorption function purifying contaminated thing of NACF in the situation that of dark or insufficient light; The in the situation that of illumination abundance, adsorption function and photo-catalysis function all can purifying contaminated things, also can realize the in-situ regeneration of carbon fiber adsorption and catalytic combustion function, greatly reduce regenerative process human and material resources, financial resources expend.Succeeding in developing for alleviating China's NACF supply deficiency of this NACF has important effect.

Accompanying drawing explanation

Fig. 1 is the XRD spectrum of ACF1 and ACF0;

Fig. 2 is the FTIR spectrum of ACF1 and ACF0;

Fig. 3 is the adsorption/desorption curve map of AFC1 and ACF0;

Fig. 4 is the clean-up effect of ACF1 and ACF0 PARA FORMALDEHYDE PRILLS(91,95) under illumination and dark adsorption conditions;

Fig. 5 is the removal effect that under illumination condition, ACF1 and ACF0 reuse 6 PARA FORMALDEHYDE PRILLS(91,95)s.

Note: photo-catalysis function NACF (being labeled as: ACF1) prepared by the present invention, and control sample NACF (being labeled as: ACF0).

The specific embodiment

embodiment 1

1) will there is the NACF that electric conductivity and resistivity are less than 80k Ω/m, boil cleaning with 2% hydrochloric acid, after again with distillation washing to neutral, and as for oven for drying 24h;

2) by step 1) in the NACF DMF solution that is placed in 0.05mol/L dicyanodiamine soak 24h;

3) process of immobilized graphite-phase carbonitride is carried out in electrolytic cell, electrochemical deposition condition: with the N of 0.05mol/L dicyanodiamine, N dimethyl formamide solution is as electrolyte, take graphite as anode, take step 2) NACF be negative electrode, power supply is dc source, electrolytic process voltage 2000V, 25 ℃ of electrolytic process temperature, electrolysis time 1h.

4) from electrolytic cell, take out the NACF of negative electrode, and fully wash, dry with distilled water, make immobilized graphite-phase carbonitride and have the NACF of photo-catalysis function.

embodiment 2

1) will there is the NACF that electric conductivity and resistivity are less than 80k Ω/m, boil cleaning with 2% hydrochloric acid, after again with distillation washing to neutral, and as for oven for drying 24h;

2) by step 1) in the NACF DMF solution that is placed in 0.15mol/L dicyanodiamine soak 24h;

3) process of immobilized graphite-phase carbonitride is carried out in electrolytic cell, electrochemical deposition condition: with the N of 0.15mol/L dicyanodiamine, N dimethyl formamide solution is as electrolyte, take graphite as anode, take step 2) NACF be negative electrode, power supply is dc source, electrolytic process voltage 500V, 30 ℃ of electrolytic process temperature, electrolysis time 5h.

4) from electrolytic cell, take out the NACF of negative electrode, and fully wash, dry with distilled water, make immobilized graphite-phase carbonitride and have the NACF of photo-catalysis function.

embodiment 3

1) will there is the NACF that electric conductivity and resistivity are less than 80k Ω/m, boil cleaning with 2% hydrochloric acid, after again with distillation washing to neutral, and as for oven for drying 24h;

2) by step 1) in the NACF DMF solution that is placed in 0.10mol/L dicyanodiamine soak 24h;

3) process of immobilized graphite-phase carbonitride is carried out in electrolytic cell, electrochemical deposition condition: with the N of 0.10mol/L dicyanodiamine, N dimethyl formamide solution is as electrolyte, take graphite as anode, take step 2) NACF be negative electrode, power supply is dc source, electrolytic process voltage 1000V, 28 ℃ of electrolytic process temperature, electrolysis time 3h.

4) from electrolytic cell, take out the NACF of negative electrode, and fully wash, dry with distilled water, make immobilized graphite-phase carbonitride and have the NACF of photo-catalysis function.

Fig. 1 is the XRD spectrum of ACF1 and ACF0.As seen from the figure, ACF1 is 2 θnear=27.65o, have a wider diffraction maximum, it is corresponding to (002) crystal face diffraction maximum of graphite-phase carbonitride.In addition, ACF1 is 2 θnear=13.23o, have a wider diffraction maximum, it is corresponding to (100) crystal face diffraction maximum of graphite-phase carbonitride.

Fig. 2 is the FTIR spectrum of ACF1 and ACF0.ACF1 is at 810nm ^-1characteristic absorption peak can be attributed to the flexural vibrations of piperazine ring, 1246 ~ 1633 nm ^-1in scope, several strong characteristic peaks are corresponding to the characteristic absorption peak of CN heterocyclic compound.1326 nm ^-1with 1635 nm ^-1the characteristic absorption peak at place is attributed to respectively the C-N key of graphite-phase carbonitride and the flexural vibrations absworption peak of C=N key.1635 nm ^-1there is stronger characteristic absorption peak explanation g-C in place ₃n ₄degree of crystallinity higher.3175 nm ^-1with 3432 nm ^-1characteristic absorption peak be respectively the stretching vibration absworption peak of N-H key and O-H key.

Fig. 3 is the N of ACF1 and ACF0 sample ₂adsorption-desorption curve map.As seen from the figure, the adsorption isotherm of two kinds of samples all presents identical type, and all has hysteresis loop.In addition, it can also be seen that from figure the adsorbance of ACF1 is slightly less than ACF0.

Fig. 4 is the clean-up effect of ACF1 and ACF0 PARA FORMALDEHYDE PRILLS(91,95) under illumination and dark adsorption conditions.As seen from the figure, the NACF of preparing with this technique not only has adsorption function, but also has photo-catalysis function.At dark adsorption conditions, the adsorbance of ACF1 is slightly less than ACF0; But the clean-up effect of ACF1 PARA FORMALDEHYDE PRILLS(91,95) is significantly better than the removal effect of ACF0 PARA FORMALDEHYDE PRILLS(91,95) under illumination condition.

Fig. 5 is the clean-up effect experiment that under illumination condition, ACF1 and ACF0 reuse 6 PARA FORMALDEHYDE PRILLS(91,95)s, and the clean-up effect of ACF1 PARA FORMALDEHYDE PRILLS(91,95) is significantly better than ACF0 as can be seen from Fig..The clearance that ACF1 reuses 6 rear PARA FORMALDEHYDE PRILLS(91,95)s under the same conditions more than 94%, and ACF0 reuse 6 times after PARA FORMALDEHYDE PRILLS(91,95) clearance be only 4%.

The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (3)

1. a preparation method with photo-catalysis function NACF, is characterized in that: the NACF that adopts the immobilized graphite-phase carbonitride of electrochemical production.

2. the preparation method with photo-catalysis function NACF according to claim 1, is characterized in that: comprise the following steps:

(1) will there is the NACF that electric conductivity and resistivity are less than 80k Ω/m, and boil after cleaning with the hydrochloric acid of 2wt.%, then be washed with distilled water to neutrality, in baking oven, dry 24h;

(2) the DMF solution that the NACF of step (1) is placed in to dicyanodiamine soaks 24h;

(3) process of immobilized graphite-phase carbonitride is carried out in electrolytic cell, electrochemical deposition condition: with the N of dicyanodiamine, N dimethyl formamide solution is as electrolyte, take graphite as anode, take the NACF of step (2) as negative electrode, power supply is dc source, electrolytic process voltage 500 ~ 2000V, 25 ~ 30 ℃ of temperature, time 1 ~ 5h;

(4) from electrolytic cell, take out the NACF of negative electrode, fully wash, dry with distilled water, make the NACF of immobilized graphite-phase carbonitride.

3. the preparation method with photo-catalysis function NACF according to claim 2, is characterized in that: in the DMF solution of described dicyanodiamine, the concentration of dicyanodiamine is 0.05 ~ 0.15mol/L.

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