BiO(HCOO)xIyBr1-x-yThe solid-phase grinding preparation method of mischcrystal photocatalyst
阅读说明：本技术 BiO(HCOO)xIyBr1-x-y固溶体光催化剂的固相研磨制备方法 (BiO(HCOO)xIyBr1-x-yThe solid-phase grinding preparation method of mischcrystal photocatalyst ) 是由 韩巧凤 彭茂媛 于 2019-08-22 设计创作，主要内容包括：本发明涉及一种室温固相研磨法制备片状溴-碘-甲酸氧铋固溶体BiO(HCOO)_xI_yBr_(1-x-y)光催化剂的方法及其性能研究,特别是采用了简单的固相研磨法,制备得到片状溴-碘-甲酸氧铋固溶体。该样品的制备方法包括以下步骤：将五水硝酸铋与甲酸钠粉末置于研钵中,常温下研磨一定时间后直接加入溴化钾研磨,再加入碘化钾继续研磨一定时间,反应结束后洗涤干燥即可得到片状溴-碘-甲酸氧铋固溶体。固溶体在降解模拟污染物罗丹明B(RhB)时具有很好效果,表明其在环境污染治理方面具有良好的应用前景。(The present invention relates to a kind of Room Temperature Solid State polishings to prepare the bromo- iodo- formic acid oxygen bismuth solid solution BiO (HCOO) of sheet x I y Br 1‑x‑y The bromo- iodo- formic acid oxygen bismuth solid solution of sheet is prepared especially with simple solid-phase sequencing in the method and its performance study of photochemical catalyst.The preparation method of the sample is the following steps are included: five water bismuth nitrates and sodium formate powder are placed in mortar, it is ground under room temperature and is directly added into potassium bromide grinding after a certain period of time, it adds potassium iodide to continue to grind certain time, the bromo- iodo- formic acid oxygen bismuth solid solution of sheet can be obtained in washing drying after reaction.Solid solution has very good effect when degrading simulating pollution object rhodamine B (RhB), shows that it has a good application prospect in terms of environmental pollution improvement.)
1. a kind of BiO (HCOO)xIyBr1-x-yThe solid-phase grinding preparation method of mischcrystal photocatalyst, it is characterised in that: the light Catalyst is prepared using following steps:
Step 1: by Bi (NO3)3·5H2O and HCOONa mixed grinding；
Step 2: KI will be added in step 1 products therefrom, KBr continues to grind；
Step 3: washing is drying to obtain sheet BiO (HCOO) after reactionxIyBr1-x-yMischcrystal photocatalyst.
2. according to the method described in claim 1, it is characterized by: the raw material Bi (NO3)3·5H2O, HCOONa, KBr with The molar ratio of KI is 1:5:0.3:0.3.
3. according to the method described in claim 1, it is characterized by: the milling time of the step 1 is 1h.
4. according to the method described in claim 1, it is characterized by: the addition KI, KBr be first be added KBr grinding 1h, then KI is added and grinds 1h.
5. according to the method described in claim 1, it is characterized by: the mixed grinding is that raw material is placed in room temperature in mortar Lower solid-phase grinding.
6. according to the method described in claim 1, it is characterized by: the washing is to make to be washed with deionized 3 times, ethyl alcohol It washes primary.
7. according to the method described in claim 1, it is characterized by: the drying temperature is room temperature.
Technical field
The invention belongs to field of inorganic nano-material preparation, are a kind of BiO (HCOO) specificallyxIyBr1-x-ySolid solution The solid-phase grinding preparation method of photochemical catalyst.
Background technique
Today's society is faced with two hang-up of energy shortage and environmental pollution, and semiconductor light-catalyst solves energy because it has Great potential on source and environmental problem and cause extensive research interest.So far, various semiconductor materials are designed At photochemical catalyst, including metal oxide, sulfide, nitride and its compound.Wherein the oxide of bismuth has [Bi2O2]2+ Layer structure, such as Bi2O3, BiOX (X=Cl, Br, I), BiVO4,Bi2WO6,Bi4Ti3O12,BiPO4,Bi2O2CO3, BiOHCOO etc..The internal electric field that this unique layer structure is formed is conducive to the separation in light induced electron and hole, to improve Its photocatalysis effect.
However the biggish forbidden bandwidth of BiOHCOO is about 3.30eV (Xiong, Cheng, et al.BiOCOOH hierarchical nanostructures:Shape-controlled solvothermal synthesis and Photocatalytic degradation performances [J] .CrystEngComm, 2011,13,2381) make it can only Photocatalytic activity is shown under the excitation of ultraviolet light, and ultraviolet light accounts for about the 5% of sunlight.Therefore expand the light of BiOHCOO Absorption region is particularly important.Up to the present, people have developed many methods to expand the light of wide band gap semiconducter Response range, including construction heterojunction structure, metal and nonmetal doping and codope, noble metal loading, crystal face design, Construct solid solution etc..Wherein, the formation of solid solution can continuously adjust band structure, to inhale in redox ability and light Reach optimum balance between receipts, photocatalytic activity is made to reach maximum.
Summary of the invention
It is an object of the invention to overcome the shortage of prior art, a kind of BiO (HCOO) is providedxIyBr1-x-ySolid solution light is urged The solid-phase grinding preparation method of agent.
The technical solution for realizing the aim of the invention is as follows: at room temperature by sequentially adding five water nitric acid of slightly water-soluble Bismuth, water-soluble sodium formate, potassium iodide, potassium bromide raw material are ground in mortar, and solid-phase grinding prepares the good BiO of crystallinity (HCOO)xIyBr1-x-yMischcrystal photocatalyst, to realize the purpose of the present invention, comprising the following steps:
Step 1: by Bi (NO3)3·5H2O and HCOONa mixed grinding certain time；
Step 2: KI being added in step 1 products therefrom, KBr continues to grind certain time；
Step 3: up to sheet BiO (HCOO) after washing is dry after reactionxIyBr1-x-yMischcrystal photocatalyst.
Milling time described in step 1 is 1h；
Grinding temperature described in step 1 is room temperature；
Described in step 2 plus sampfe order is first potassium iodide, rear potassium bromide；
Described in step 2 plus potassium iodide milling time is 1h, and adding potassium bromide milling time is 1h, and grinding temperature is room temperature；
Step 1 and 2 described plus Bi (NO3)3·5H2The molar ratio of O, HCOONa, KBr, KI are 1:5:0.2:0.2 to 1:5: 0.4:0.4。
Mode of washing described in step 3 is washing 3 times, and ethyl alcohol is washed 1 time；
Drying temperature described in step 3 is room temperature；
Preferred plan of the present invention are as follows:
Step 1: by Bi (NO3)3·5H2O and HCOONa mixed grinding 1.0h；
Step 2: sequentially adding 0.3mmolKI grinding 1.0h in step 1 products therefrom, add 0.3mmolKBr
Continue to grind；
Step 3: washed after reaction up to sheet BiO (HCOO)0.4I0.3Br0.3Mischcrystal photocatalyst.
The present invention has following remarkable advantage:
1, this method is simple, and experimental period is short, saves the time, and yield is high.It is not necessary that any template is added, five water are used only Bismuth nitrate, sodium formate, potassium bromide, potassium iodide raw material have obtained BiO (HCOO)xIyBr1-x-ySolid solution；
2, the BiO (HCOO) obtained by the present inventionxIyBr1-x-yFor sheet；
3, this it is nanocrystalline excellent visible light photocatalytic degradation performance is shown to rhodamine B (RhB), in industrial wastewater treatment Field has good application.
Detailed description of the invention
Fig. 1 is present invention preparation sheet BiO (HCOO)xIyBr1-x-yThe flow diagram of solid solution.
Fig. 2 is embodiment 1BiO (HCOO)0.4I0.3Br0.3The nanocrystalline transmission electron microscope picture of gained.
Fig. 3 is 1 gained sample XRD spectra of embodiment.
Fig. 4 is 1 gained sample XRD spectra of comparative example.
Fig. 5 is 2 gained sample XRD spectra of comparative example.
Fig. 6 is the rhodamine B degradation figure of 20mg/L of degrading under visible light to the sample of embodiment 1-3 and comparative example 1-3.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and detailed description.
In conjunction with Fig. 1, the present invention has the BiO (HCOO) of unique morphology using polishing preparationxIyBr1-x-yThe side of catalyst Method, feature the following steps are included:
Step 1: by Bi (NO3)3·5H2O and HCOONa mixed grinding certain time；
Step 2: KI will be added in step 1 products therefrom, KBr continues to grind；
Step 3: washed after reaction up to sheet BiO (HCOO)xIyBr1-x-yMischcrystal photocatalyst.
Below with reference to embodiment, comparative example, the present invention will be further described in detail for attached drawing: