CN103769050B - Electrochemical production photo-catalysis function NACF - Google Patents

Abstract

The invention discloses a kind of preparation method with photo-catalysis function NACF, with NACF, dicyanodiamine, DMF etc. for primary raw material, obtained the NACF of immobilized graphite phase carbon nitride by electrochemical deposition method.This NACF not only has adsorption function, and has photo-catalysis function.It relies on the adsorption function purifying contaminated thing of NACF when dark or insufficient light; When 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 of this NACF has important effect for alleviation China NACF supply deficiency.

Description

Electrochemical production photo-catalysis function NACF

Technical field

The invention belongs to NACF preparation field, be specifically related to a kind of to there is the preparation method that light urges functional activity Carbon fibe.

Background technology

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

Due to NACF to the absorption of pollutant mainly based on micropore filling, adsorbance is limited, can reach in short time and adsorb saturated and lose adsorption capacity, adsorbing saturated NACF becomes secondary pollution source, and must carry out regeneration process to it can utilize again.Current NACF renovation process can be divided into two classes generally: one is manage to make adsorbate desorption, namely by creating the condition corresponding with underload (introduce material or energy and make reaction force attenuation between adsorption molecule and NACF or disappearance), adsorbate is removed; Two is the structures relying on thermal decomposition or redox reaction to destroy adsorbate, removing adsorbate.Traditional renovation process mainly contains hot recycling, 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 the focus that a kind of renovation process at normal temperature, normal pressure, low cost, high efficiency, operating procedure Dan Jian becomes research is both at home and abroad studied.

Summary of the invention

The object of the present invention is to provide and a kind of there is the preparation method that light urges functional activity Carbon fibe.The photo-catalysis function NACF that the present invention obtains has photo-catalysis function and adsorption function, and NACF can in-situ regeneration under light illumination.

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

Adopt the NACF of the immobilized graphite phase carbon nitride of electrochemical production, comprise the following steps:

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

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

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

(4) from electrolytic cell, take out the NACF of negative electrode, fully wash with distilled water, dry, be i.e. the NACF of obtained immobilized graphite phase carbon nitride.

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 obtains not only has adsorption function, and has photo-catalysis function.It relies on the adsorption function purifying contaminated thing of NACF when dark or insufficient light; When 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 of this NACF has important effect for alleviation China NACF supply deficiency.

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 reuses 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).

Detailed description of the invention

embodiment 1

1) will electric conductivity be had and the resistivity NACF that is less than 80k Ω/m, boil cleaning with the hydrochloric acid of 2%, after again with distillation washing to neutral, and as 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 carbon nitride is carried out in electrolytic cell, electrochemical deposition condition: with the N of 0.05mol/L dicyanodiamine, N-dimethylformamide solution is as electrolyte, take graphite as anode, with step 2) NACF be negative electrode, power supply is dc source, electrolytic process voltage 2000V, electrolytic process temperature 25 DEG C, electrolysis time 1h.

4) from electrolytic cell, take out the NACF of negative electrode, and fully wash with distilled water, dry, namely obtained immobilized graphite phase carbon nitride has the NACF of photo-catalysis function.

embodiment 2

1) will electric conductivity be had and the resistivity NACF that is less than 80k Ω/m, boil cleaning with the hydrochloric acid of 2%, after again with distillation washing to neutral, and as 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 carbon nitride is carried out in electrolytic cell, electrochemical deposition condition: with the N of 0.15mol/L dicyanodiamine, N-dimethylformamide solution is as electrolyte, take graphite as anode, with step 2) NACF be negative electrode, power supply is dc source, electrolytic process voltage 500V, electrolytic process temperature 30 DEG C, electrolysis time 5h.

4) from electrolytic cell, take out the NACF of negative electrode, and fully wash with distilled water, dry, namely obtained immobilized graphite phase carbon nitride has the NACF of photo-catalysis function.

embodiment 3

1) will electric conductivity be had and the resistivity NACF that is less than 80k Ω/m, boil cleaning with the hydrochloric acid of 2%, after again with distillation washing to neutral, and as 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 carbon nitride is carried out in electrolytic cell, electrochemical deposition condition: with the N of 0.10mol/L dicyanodiamine, N-dimethylformamide solution is as electrolyte, take graphite as anode, with step 2) NACF be negative electrode, power supply is dc source, electrolytic process voltage 1000V, electrolytic process temperature 28 DEG C, electrolysis time 3h.

4) from electrolytic cell, take out the NACF of negative electrode, and fully wash with distilled water, dry, namely obtained immobilized graphite phase carbon nitride has the NACF of photo-catalysis function.

Fig. 1 is the XRD spectrum of ACF1 and ACF0.As seen from the figure, ACF1 is 2 θhave the diffraction maximum that wider near=27.65o, it corresponds to (002) crystallographic plane diffraction peak of graphite phase carbon nitride.In addition, ACF1 is 2 θhave the diffraction maximum that wider near=13.23o, it corresponds to (100) crystallographic plane diffraction peak of graphite phase carbon nitride.

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 peak corresponds to the characteristic absorption peak of CN heterocyclic compound.1326 nm ^-1with 1635 nm ^-1the characteristic absorption peak at place is attributed to the C-N key of graphite phase carbon nitride and the flexural vibrations absworption peak of C=N key respectively.1635 nm ^-1place occurs that stronger characteristic absorption peak illustrates g-C 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 the adsorbance of ACF1 is slightly less than ACF0 from figure.

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, not only there is adsorption function with NACF prepared by this technique, but also there is 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 reuses 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..ACF1 reuses the clearance of PARA FORMALDEHYDE PRILLS(91,95)s after 6 more than 94% under the same conditions, 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 done 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 (2)

1. there is a preparation method for photo-catalysis function NACF, it is characterized in that: the NACF adopting the immobilized graphite phase carbon nitride of electrochemical production;

Comprise the following steps:

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

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

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

(4) from electrolytic cell, take out the NACF of negative electrode, fully wash with distilled water, dry, be i.e. the NACF of obtained immobilized graphite phase carbon nitride.

2. the preparation method with photo-catalysis function NACF according to claim 1, is characterized in that: in the DMF solution of described dicyanodiamine, the concentration of dicyanodiamine is 0.05 ~ 0.15mol/L.