A kind of Ni/CeO2/g-C3N4Composite material and its application in photocatalysisTechnical field
The invention belongs to material and photocatalysis fields, and in particular to a kind of Ni/CeO2/g-C3N4Composite material and its in lightApplication in catalysis.
Background technique
Water is that the mankind depend on for existence indispensable resource, and water pollution problems annoyings always people, chloracetic acid(HAAs) especially trichloroacetic acid (TCAA) industry, agriculturally be widely used and water sterilization during main disinfection pairProduct has strong carcinogenicity, seriously threatens the life security of the mankind.Prior inventions people has found a kind of ceria/graphite-phase60min can make the degradation rate of TCAA in water up to 52% to nitridation carbon composite under visible light, in order to further increase titanium dioxideFor cerium/graphite phase carbon nitride composite material to TCAA catalytic degradation activity, the present invention provides a kind of ceria-graphite of nickel dopingPhase carbon nitride composite material, under visible light, can effectively degrade the material TCAA, it is seen that 45min under light, degradation rate is up to 86%.
Summary of the invention
The present invention provides a kind of Ni/CeO2/g-C3N4Composite material, it is characterised in that the Ni/CeO2/g-C3N4Composite woodThe preparation method of material includes the following steps:
(1) it after grinding cyanamid dimerization, melamine in mortar uniformly, is placed in Muffle furnace, with the speed of 10 DEG C/minAfter rate is warming up to 550 DEG C, heat preservation 5 hours, room temperature is down to get g-C with the rate of 5 DEG C/min3N4；
(2) cerous nitrate, nickel nitrate are dissolved in deionized water, g-C obtained in step (1) is added3N4, urea andAfter EDTA is heated to 150 DEG C, heat preservation 12 hours in autoclave, cooled to room temperature, filtering, precipitating use deionizationAfter water, dehydrated alcohol washing, it is dried in vacuo up to the Ni/CeO2/g-C3N4Composite material (it is spare to be ground into fine powder).
Cyanamid dimerization in step (1), melamine molar ratio be 1:1；Cerous nitrate and nickel nitrate rubs in step (2)You are than being 1:0.1, every gram of g-C3N4Using cerous nitrate 1mmol, the molar ratio of urea and cerous nitrate is 1:1, mole of ureaDosage is 2 times of EDTA.
Another embodiment of the present invention provides above-mentioned Ni/CeO2/g-C3N4The preparation method of composite material, feature existIn including the following steps:
(1) it after grinding cyanamid dimerization, melamine in mortar uniformly, is placed in Muffle furnace, with the speed of 10 DEG C/minAfter rate is warming up to 550 DEG C, heat preservation 5 hours, room temperature is down to get g-C with the rate of 5 DEG C/min3N4；
(2) cerous nitrate, nickel nitrate are dissolved in deionized water, g-C obtained in step (1) is added3N4, urea andAfter EDTA is heated to 150 DEG C, heat preservation 12 hours in autoclave, cooled to room temperature, filtering, precipitating use deionizationAfter water, dehydrated alcohol washing, it is dried in vacuo up to the Ni/CeO2/g-C3N4Composite material (it is spare to be ground into fine powder).
Cyanamid dimerization in step (1), melamine molar ratio be 1:1；Cerous nitrate and nickel nitrate rubs in step (2)You are than being 1:0.1, every gram of g-C3N4Using cerous nitrate 1mmol, the molar ratio of urea and cerous nitrate is 1:1, mole of ureaDosage is 2 times of EDTA.
Another embodiment of the present invention provides above-mentioned Ni/CeO2/g-C3N4Composite material is in photocatalytic degradation trichloroacetic acidIn application.
Compared with the prior art, the advantages of the present invention are as follows: the present invention adulterates to obtain a kind of Ni/CeO by nickel2/g-C3N4Composite material, under visible light, can effectively degrade the material TCAA, it is seen that 45min under light, degradation rate is up to 86%.
Detailed description of the invention
Fig. 1 is g-C prepared by embodiment 13N4SEM figure；
Fig. 2 is the SEM figure of product A；
Fig. 3 is g-C prepared by embodiment 23N4SEM figure；
Fig. 4 is product A-C, g-C3N4Photocatalytic degradation TCAA effect picture.
Specific embodiment
For the ease of a further understanding of the present invention, examples provided below has done more detailed description to it.ButIt is that these embodiments are only not supposed to be a limitation to the present invention or implementation principle for better understanding invention, reality of the inventionThe mode of applying is not limited to the following contents.
Embodiment 1
(1) after grinding cyanamid dimerization (10mmol), melamine (10mmol) in mortar uniformly, it is placed in Muffle furnaceIn, after being warming up to 550 DEG C, heat preservation 5 hours with the rate of 10 DEG C/min, room temperature is down to get g-C with the rate of 5 DEG C/min3N4(Fig. 1)；
(2) cerous nitrate (1mmol), nickel nitrate (0.1mmol) are dissolved in deionized water (15mL), g-C is added3N4(1.0g, step (1) preparation), urea (1.0mmol) and EDTA (0.5mmol), are heated to 150 DEG C in autoclave,After heat preservation 12 hours, cooled to room temperature, filtering are dried in vacuo after precipitating deionized water, dehydrated alcohol wash up to instituteState Ni/CeO2/g-C3N4Composite material (hereinafter referred to as product A, Fig. 2, it is spare to be ground into fine powder).
Embodiment 2
(1) it after grinding melamine (20mmol) in mortar uniformly, is placed in Muffle furnace, with the rate of 10 DEG C/minAfter being warming up to 550 DEG C, heat preservation 5 hours, room temperature is down to get g-C with the rate of 5 DEG C/min3N4(Fig. 3)；
(2) cerous nitrate (1mmol), nickel nitrate (0.1mmol) are dissolved in deionized water (15mL), g-C is added3N4(1.0g, step (1) preparation), urea (1.0mmol) and EDTA (0.5mmol), are heated to 150 DEG C in autoclave,After heat preservation 12 hours, cooled to room temperature, filtering are dried in vacuo after precipitating deionized water, dehydrated alcohol wash to obtain the final productNi/CeO2/g-C3N4Composite material (hereinafter referred to as product B, it is spare to be ground into fine powder).
Embodiment 3
Cerous nitrate (1mmol) is dissolved in deionized water (15mL), g-C is added3N4(1.0g, step (1) preparation),Urea (1.0mmol) and EDTA (0.5mmol), after 150 DEG C, heat preservation 12 hours are heated in autoclave, natural coolingTo room temperature, filtering, after precipitating deionized water, dehydrated alcohol wash, it is dried in vacuo up to CeO2/g-C3N4Composite material is (followingAbbreviation products C, it is spare to be ground into fine powder).
4 trichloroacetic acid degradation experiment of embodiment
It configures the TCAA solution (pH about 5.5-5.6,4 parts) that 200ml initial concentration is 2.0mg/L and is separately added into 0.2g productA、B、C、g-C3N4(prepared by embodiment 1), using 500W xenon lamp and 420nm optical filter as visible light source, first in dark room conditionsIt is respectively stirred to react 45min, then turns on light and is stirred to react 45min；According to document (Wang Fen, etc., environmental project journal, the 9th phase of volume 9,2015,4153-4158) record analysis method, every 15min, with TCAA concentration calculation degradation rate in HPLC analytical solution.The experimental results showed that degradation effect product A > B > C, g-C of TCAA3N4To TCAA without degradation (Fig. 4), product A is to TCAADegradation effect is best, after illumination 45min, to the degradation rate of TCAA up to 86%.