CN104826637A - Preparation method of BiOBr/Bi2O3 heterojunction composite catalyst - Google Patents

Preparation method of BiOBr/Bi2O3 heterojunction composite catalyst Download PDF

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CN104826637A
CN104826637A CN201510070040.8A CN201510070040A CN104826637A CN 104826637 A CN104826637 A CN 104826637A CN 201510070040 A CN201510070040 A CN 201510070040A CN 104826637 A CN104826637 A CN 104826637A
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biobr
catalyst
bi2o3
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composite catalyst
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CN104826637B (en
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王其召
焦丹花
张淑玲
杜仲奕
杨文娟
俞洁
苏碧桃
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Northwest Normal University
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Abstract

The invention relates to a preparation method of a BiOBr/Bi2O3 heterojunction composite catalyst and belongs to the technical field of composite materials and photocatalysis. In the method, through in-situ hydrolysis on the surface of Bi2O3 to synthesize BiOBr, the BiOBr/Bi2O3, of which the surface is in a layered 3D nano-structure, is formed, wherein the support capacity of the BiOBr in the composite catalyst can be regulated through adjustment of the pH of the system and the molar ratio of Bi2O3 to HB3. An experimental result proves that when the pH of the system is 4-8 and the molar ratio of Bi2O3 to HB3 is 1:1.4-1:2, the support capacity of the BiOBr/Bi2O3 composite catalyst is 65-85%, wherein an excellent photo-catalytic performance is achieved when the support capacity of BiOBr is in the range. The catalyst has application potential in the field of waste water treatment and organic pollutant degradation. In addition, the catalyst is very easy to separate and is free of obvious loss after three times of recycle usage.

Description

BiOBr/Bi 2o 3the preparation method of hetero-junctions composite catalyst
Technical field
The invention belongs to field of compound material and photocatalysis technology field, relate to a kind of BiOBr/Bi 2o 3the preparation method of hetero-junctions composite catalyst.
Background technology
Along with global pollution and energy shortage problem, find sunshine has become society study hotspot as the environmental treatment technology of direct energy source; As environmentally friendly photochemical catalyst, semi-conducting material is attract the sight of more and more people.Since Honda-Fujishima in 1972 finds photochemistry electrode, TiO 2breakthrough progress has been achieved as the most popular research material in the time of nearly half a century in the past.Along with deepening continuously of research, scientists have also discovered simultaneously much can the photochemical catalyst of more good utilisation sunshine: Ag/AgBr/BiOBr, Bi/BiOCl, Mn-BiOBr, Fe 3o 4/ BiOCl, Bi 2s 3/ BiOCl, Bi 2o 3/ BiOCl, BiOCl/BiVO 4and BiOBr-g-C 3n 4deng.As time goes by, Bi base semiconductor catalysis material is done washing with the layer structure of its excellence and good chemical stability the sight of this more and more people.
Use the organic pollution in photocatalyst for degrading water body to achieve certain achievement in research at previous decades, traditional photocatalytic process comprises: the chemical reaction producing light induced electron and hole respectively and occur on catalyst surface afterwards on conduction band and valence band.For the degraded of dyestuff, the catalytic mechanism that still existence three kinds is possible: photocatalysis, photoactivate, photodissociation.The factor affecting degradating organic dye also has a lot, comprises the concentration of compound, the kind of electrodeless ion, reaction temperature and pH etc.In numerous semiconductor light-catalyst had compared with low energy gap width, Bi 2o 3with its energy gap in the unquestionable only choosing becoming new Shanxi photochemical catalyst of 2.4-2.8.
BiOBr is a kind of indirect semiconductor material, and its band system can be about 2.69eV, and does not change by the impact of synthesis condition.And the pattern of BiOBr material and degree of crystallinity depend on the temperature and time of Hydrothermal Synthesis.In the process of degraded methyl orange dye, this sheet BiOBr demonstrates very high first catalytic activity.Therefore, by BiOBr and Bi 2o 3be compounded to form the composite of a fixed structure and pattern, make BiOBr and Bi 2o 3photocatalysis performance produce collaborative, obtain the material of excellent catalytic performance, be expected to there is application prospect in the degraded of wastewater treatment and organic pollution.
Summary of the invention
The object of this invention is to provide a kind of BiOBr/Bi 2o 3the preparation method of hetero-junctions composite catalyst.
One, BiOBr/Bi 2o 3the preparation of hetero-junctions composite catalyst
We know, the pattern of photocatalysis performance and material, size, structural nexus are tight, and the pattern of composite, structure depend on its preparation method.BiOBr/Bi of the present invention 2o 3the preparation of hetero-junctions composite catalyst is by Bi 2o 3surface in situ hydrolysis BiOBr, forms the BiOBr/Bi that surface is stratiform 3D nanostructured 2o 3.Concrete preparation technology is: by Bi 2o 3fully be dissolved in HBr solution, regulate pH=4-8 with ammoniacal liquor, in 40 ~ 50 DEG C of stirring reaction 0.5 ~ 1 h, centrifugal, washing, after drying, at 200 ~ 400 DEG C, high-temperature calcination 1 ~ 4 h, obtains BiOBr/Bi 2o 3hetero-junctions composite catalyst.
In above-mentioned HBr solution, the concentration of HBr is 0.4 ~ 0.6 molL -1hBr.
The present invention is by adjusting pH and Bi of system 2o 3composite catalyst BiOBr/Bi is adjusted with the mol ratio of HBr 2o 3the load capacity of middle BiOBr.Experiment shows, at the pH=4-8 of adjustment system, Bi 2o 3when being 1:1.4 ~ 1:2 with the mol ratio of HBr, composite catalyst BiOBr/Bi 2o 3the load capacity of middle BiOBr is between 65 ~ 85%, and BiOBr is in this loading range, shows excellent photocatalysis performance.
Two, the crystal structure of catalyst and morphology analysis
1, XRD analysis
Fig. 1 is XRD figure: (a) Bi of catalyst 2o 3; (b) 85% BiOBr/Bi 2o 3, pH=6; (c) 75% BiOBr/Bi 2o 3, pH=4; (d) 75% BiOBr/Bi 2o 3, pH=6; (e) 75% BiOBr/Bi 2o 3, pH=8; (f) 65% BiOBr/Bi 2o 3, pH=6.(g)BiOBr。As can be seen from Figure 1, the BiOBr/Bi of different loads amount 2o 3all there is similar diffraction maximum in compound.As Fig. 1 a, synthesis can be corresponding with (120) (200) crystal face in standard card JCPDS:No. 41-1449 with the diffraction maximum that 33.2 ° occur respectively at 27.4 °, there is no other diffraction maximums occur.BiOBr and the standard card JCPDS:No.73-2061 of synthesis compare, and belong to tetragonal phase, also do not occur other impurity peaks, contrast all compounds, and we find, Bi 2o 3existence do not make the crystal formation of compound change.
2, sem analysis
Fig. 2 is SEM figure: (a) pure Bi of catalyst 2o 3; (b) pure BiOBr; (c) BiOBr/Bi 2o 3, as can be seen from Fig. 2 a, Bi 2o 3be made up of the nanometer sheet of uniform 2 μm, but dispersiveness is not fine.But scheme us from b and can see, the favorable dispersibility of BiOBr, whole pattern presents the structure of single flower-like nanometer sheet, and diameter is comparatively large, at about 5 μm.Fig. 2 (c) shows, the pattern of compound is the 3D layered nano-structure of diameter at the lamellar structure composition of 2 ~ 5 μm, these particles are made up of irregular smooth nanometer sheet, and the coarse surface formed may increase its specific area, are conducive to improving its photocatalysis performance.
3, infrared spectrum analysis
Fig. 3 is BiOBr and 75% pH=6 BiOBr/Bi 2o 3infrared spectrogram.As can be seen from Figure 3, at BiOBr and 75% pH=6 BiOBr/Bi 2o 3infrared spectrogram in, 520 cm -1the strongest peak occurred belongs to the vibration peak of Bi-O chemical bond in BiOBr; And 75% pH=6 BiOBr/Bi 2o 3at 432 cm -1that occur is then Bi 2o 3characteristic peak.75% BiOBr/Bi 2o 3middle BiOBr and Bi simultaneously occurred 2o 3characteristic peak can prove that it exists.
4, UV Diffuse Reflectance Spectroscopy analysis
Fig. 4 is the UV Diffuse Reflectance Spectroscopy of synthetic catalyst of the present invention.Shown in Fig. 4, compared to the data reported, the ABSORPTION EDGE of BiOBr has the trend of red shift, and this may be relevant with synthetic method.BiOBr/Bi 2o 3the ABSORPTION EDGE of compound is equally at visible region, and compared to pure BiOBr, ABSORPTION EDGE shows the trend of expansion.The ABSORPTION EDGE of pure BiOBr is at 455 nm, and corresponding energy gap is 2.68 eV, and compound of the present invention has the trend of red shift in the ABSORPTION EDGE of visible region, and energy gap is too narrow to 2.12 eV (shown in Fig. 5) most.These phenomenons show, the architectural feature of hetero-junctions really can be brought out and be produced more light induced electron and hole, and perhaps this can improve its photocatalysis performance.
6, nitrogen adsorption desorption test
The specific surface area size of sample and pore-size distribution obtain by the test of nitrogen adsorption desorption.Table 1 is the specific area of sample, pore volume, aperture and energy gap tables of data.
From the data of table 1,75% BiOBr/Bi 2o 3(pH=6) specific area of sample is 49.96 m 2g -1, be greater than other sample, as can be seen from graph of pore diameter distribution, BiOBr and Bi 2o 3average pore size be distributed in 10 ~ 25 nm, and the pore-size distribution of all the other compounds is at 5 ~ 12 nm.Comprehensively all data, 75% BiOBr/Bi 2o 3(pH=6) specific area of sample is maximum, and aperture is also less, and therefore we infer, this sample may have the most excellent catalytic performance.
Three, the absorption of catalyst and degradation property test
1, photocatalytic degradation capability test
Adopt methyl orange organic molecule as BiOBr/Bi 2o 3the test of compound photocatalyst for degrading ability: get 60 mg catalyst in the methyl orange aqueous solution (10 mg/L) of 60 mL, after ultrasonic 5 minutes, dark reaction 30 min is to ensure to reach adsorption-desorption balance, irradiate at the Xe lamp (λ > 420 nm optical filter) of 300W afterwards, whole course of reaction is all at room temperature carried out, be placed in 7000 revs/min, centrifuge centrifugal 3 minutes getting 5-6 mL solution after different irradiation times, get supernatant, use ultraviolet specrophotometer to test its concentration.
Fig. 6 is different catalysts methyl orange concentration (MO) concentration (C/C in visible ray (λ > 420 nm) catalytic degradation process 0) time history plot.Original methyl orange concentration is for starting concentration (C 0), as can be seen from Figure 6, under the irradiation of visible ray, the reduction degree of MO concentration is clearly.After dark reaction 30 min, reaction reaches adsorption desorption balance.After radiation of visible light 48 min, 75% BiOBr/Bi 2o 3(pH=6) be 93.8% to the removal rate of methyl orange, however under identical experiment condition 85% BiOBr/Bi 2o 3(pH=6) and 65% BiOBr/Bi 2o 3(pH=6) 73% and 70% are respectively to the removal rate of methyl orange.Result shows, BiOBr/Bi 2o 3load percentage in the nanostructured of compound hetero-junctions directly can affect the degradation capability of catalyst to methyl orange.From Fig. 6, we can obtain a result, and the degradation effect of catalyst to methyl orange is respectively: 75 % BiOBr/Bi 2o 3pH=6 (ca. 93.8%) > 75% BiOBr/Bi 2o 3pH=8 (ca. 86%) >75% BiOBr/Bi 2o 3pH=4 (ca.82%; ) Bi that BiOBr (ca.80%) > that > is pure is pure 2o 3(ca.77%) > 85% BiOBr/Bi 2o 3pH=6 (ca.73%) > 65% BiOBr/Bi 2o 3pH=6 (ca.70%).These results show, BiOBr/Bi 2o 3if Bi in compound 2o 3quantity not sufficient, just can not effectively be separated light induced electron and hole, also just can not high photo-catalysis capability.On the other hand, excessive Bi 2o 3also likely photocatalysis efficiency is reduced, because excessive Bi 2o 3likely become the complex centre in light induced electron and hole.
2, the acid-base value of solution is for the impact of photo-catalysis capability
In this experiment, we have studied the impact of acid-base value for photo-catalysis capability of solution equally.When regulate pH be 4,6,8 not etc. time, the photo-catalysis capability of catalyst is also different, this may be relevant with the degree of crystallinity of sample, the XRD phenetic analysis of catalyst in corresponding diagram 1, when pH is adjusted to 6 from 4, photo-catalysis capability reduces, the intensity of the characteristic peak of corresponding (120) crystal face also reduces, when being adjusted to 8, photo-catalysis capability improves, and the intensity of the characteristic peak of corresponding (120) crystal face also enhances.
Under institute's test condition, the degradation rate of methyl orange obeys first order reaction rule:
r = dc/dt = kKc/(1+Kc)
R represents degradation rate, and c represents the concentration of methyl orange after the reaction t time, and t is the reaction time, and k represents speed constant, and K represents and the synergistic absorption constant of reaction, and as initial concentration very little (0.01 g/L), formula above can be reduced to
ln(c 0/c) = kKt = k appt
K apprepresent first order reaction speed constant.
The k calculated in this test appas shown in Figure 7,75 % BiOBr/Bi 2o 3observed rate constant be greater than other catalyst, be about 0.0462 min -1, compared to 1.83 times of pure BiOBr.Along with the increase of BiOBr load percentage, the catalytic performance of catalyst also improves gradually, declines to some extent again after reaching optimal proportion.
3, the different light time is for the impact of photo-catalysis capability
In order to study Adsorption of Methyl Orange degradation process further, we have studied catalyst figure sample of the present invention ultraviolet-visible absorption spectroscopy figure under the different light time.Fig. 8 is 75 % BiOBr/Bi 2o 3pH=6 sample methyl orange absorption spectrum in absorption degradation process is schemed over time.Obviously can see there is an absworption peak at 464 nm places from Fig. 8, along with the prolongation of radiation of visible light time, the intensity of absworption peak reduces gradually and occurs the trend of blue shift, and the color of corresponding methyl orange also becomes colourless gradually from orange.According in document, this blue-shifted phenomenon is because in photocatalytic process, methyl orange is intermediate product by light degradation mostly, afterwards the intermediate product cause that is degraded of part again.This is sufficient proof BiOBr/Bi again 2o 3compound has excellent catalytic capability to methyl orange under the irradiation of visible ray.
4, spectrofluorimetry
Adopt spectrofluorimetry compound BiOBr/Bi 2o 3the recombination probability right with pure BiOBr photo-generate electron-hole, we also can infer the size of semi-conducting material photocatalysis performance accordingly.Fig. 9 is the luminescence generated by light figure of catalyst.As we can see from the figure, when excitation wavelength is 320 nm, BiOBr/Bi 2o 3and Bi 2o 3all occur stronger absworption peak at 430 nm places, compared to pure BiOBr, the intensity of emission peak obviously weakens, illustrates and between existence heterojunction structure construct the recombination probability really reducing light induced electron and hole.
5, the chemical stability test of catalyst
Whether catalyst is stable is the important indicator weighing its researching value, in order to verify its stability, carried out the circulation experiment of photocatalytic degradation MO, the MO solution constant volume adding isodose after each circular response terminates, to same volume, enters the circular response of next round after adsorption equilibrium.Figure 10 is 75 % BiOBr/Bi 2o 3pH=6 catalytic cycle experimental result picture, catalytic cycle still remains good catalytic activity after using three times, shows that catalyst stabilization is better, has researching value.
6, photocatalytic mechanism is explained
From document, the pollutant that BiOBr can effectively degrade in organic water body under the irradiation of ultraviolet light.For the analysis of causes of the excellent performance of the photochemical catalyst of the present invention's synthesis, a kind of reason may be that the pattern owing to having layer structure makes its specific area larger, more dyestuff can be adsorbed, specific area is large simultaneously, more avtive spot can be increased, thus be conducive to the raising of photocatalysis performance.On the other hand, due to photocatalytic process be based on Pair production compound be separated, and the right compound in the bandgap structure of catalyst and light induced electron and hole be separated closely bound up.The position of semiconductor valence band can be calculated by following formula: E vB=X – E e+ 0.5 Eg, E vBrepresent the edge current potential of valence band, X represents the electronegativity of semiconductor, and it is electronegative geometric mean of all atoms of composition semiconductor, E erepresent standard energy (being about 4.5 eV) of the free electron of hydrogen, Eg represents the band gap width of semiconductor, and therefore, the edge current potential of rewinding can pass through E cB=E vB– Eg calculates, and accordingly, valence band location is at-0.39 Ev and-0.29 eV.Electronics and hole between different semiconductors while transfer add life-span of carrier, improve the efficiency of catalyst surface Charger transfer, therefore, the transmission in the join hole of constructed hetero-junctions can effectively improve.In addition, as the key reaction part in catalytic reaction, BiOBr is positioned at the outside of compound, and therefore, reactivity site is not limited to the forming position of hetero-junctions.
Accompanying drawing explanation
Fig. 1 is XRD figure: (a) Bi of catalyst 2o 3; (b) 85% BiOBr/Bi 2o 3, pH=6; (c) 75% BiOBr/Bi 2o 3, pH=4; (d) 75% BiOBr/Bi 2o 3, pH=6; (e) 75% BiOBr/Bi 2o 3, pH=8; (f) 65% BiOBr/Bi 2o 3, pH=6; (g) BiOBr.
Fig. 2 is SEM figure: (a) pure Bi of catalyst 2o 3; (b) pure BiOBr; (c) 85% BiOBr/Bi 2o 3, pH=6.
Fig. 3 is BiOBr and 75% pH=6 BiOBr/Bi 2o 3infrared spectrogram.
Fig. 4 is the uv drs figure of catalyst.
Fig. 5 is the energy gap figure of catalyst.
Fig. 6 be catalyst at visible ray at the degradation effect figure to methyl orange.
Fig. 7 is the observed rate constant figure of catalyst.
Fig. 8 is 75 % BiOBr/Bi 2o 3pH=6 sample is ultraviolet-visible absorption spectroscopy figure under the different light time.
Fig. 9 is the luminescence generated by light figure of catalyst.
Figure 10 is 75 % BiOBr/Bi 2o 3the loop test figure of pH=6 sample.
Detailed description of the invention
embodiment 1
(1) bismuth oxide (Bi 2o 3) preparation: by 2.425 g Bi (NO 3) 35H 2mortar is put into, mixed grinding, until there is yellow powder together with O with 0.6g NaOH; Then this yellow powder is dissolved in the beaker that 30 ml distilled water are housed, after 60 DEG C of stirring in water bath 5 h, washs 3-5 time respectively with distilled water and ethanol, 80 DEG C of dryings, obtain yellow Bi 2o 3powder.
(2) BiOBr/Bi 2o 3the preparation of compound: get 0.8 g Bi 2o 3be dissolved in 0.5 molL of 15.6 ml -1in HBr, vigorous stirring, makes it to dissolve completely; Afterwards, regulate pH=8 with diluted concentrated ammonia liquor, after stirring 15 minutes, 40 DEG C of stirring in water bath 0.5 h, after centrifugal, washing, drying, by the pulverulent solids obtained; Put into crucible, proceed to Muffle furnace 300 DEG C calcining 1 h, obtain BiOBr/Bi 2o 3compound.In compound, the mass percent of BiOBr is 85%, Bi 2o 3mass percent be 15% (be denoted as 85% BiOBr/Bi 2o 3).Be 73% to the degradation rate of methyl orange.
Embodiment 2
(1) bismuth oxide (Bi 2o 3) preparation: with embodiment 1.
(2) BiOBr/Bi 2o 3the preparation of compound: get 0.8 g Bi 2o 3be dissolved in 0.5 molL of 13.6 ml -1in HBr, vigorous stirring, makes it to dissolve completely; Afterwards, regulate pH=6 with diluted concentrated ammonia liquor, after stirring 15 minutes, 40 DEG C of stirring in water bath 0.5 h, after centrifugal, washing, drying, by the pulverulent solids obtained; Put into crucible, proceed to Muffle furnace 300 DEG C calcining 1 h, obtain BiOBr/Bi 2o 3compound.In compound, the mass percent of BiOBr is 75%, Bi 2o 3mass percent be 25% (be denoted as 75% BiOBr/Bi 2o 3).Be 93.8% to the degradation rate of methyl orange.
Embodiment 3
(1) bismuth oxide (Bi 2o 3) preparation: with embodiment 1.
(2) BiOBr/Bi 2o 3the preparation of compound: get 0.8 g Bi 2o 3be dissolved in 0.5 molL of 13.6 ml -1in HBr, vigorous stirring, makes it to dissolve completely; Afterwards, regulate pH=4 with diluted concentrated ammonia liquor, after stirring 15 minutes, 40 DEG C of stirring in water bath 0.5 h, after centrifugal, washing, drying, by the pulverulent solids obtained; Put into crucible, proceed to Muffle furnace 300 DEG C calcining 1 h, obtain BiOBr/Bi 2o 3compound.In compound, the mass percent of BiOBr is 75%, Bi 2o 3mass percent be 25% (be denoted as 75% BiOBr/Bi 2o 3).Be 82% to the degradation rate of methyl orange.
Embodiment 4
(1) bismuth oxide (Bi 2o 3) preparation: with embodiment 1.
(2) BiOBr/Bi 2o 3the preparation of compound: get 0.8 g Bi 2o 3be dissolved in 0.5 molL of 13.6 ml -1in HBr, vigorous stirring, makes it to dissolve completely; Afterwards, regulate pH=8 with diluted concentrated ammonia liquor, after stirring 15 minutes, 40 DEG C of stirring in water bath 0.5 h, after centrifugal, washing, drying, by the pulverulent solids obtained; Put into crucible, proceed to Muffle furnace 300 DEG C calcining 1 h, obtain BiOBr/Bi 2o 3compound.In compound, the mass percent of BiOBr is 75%, Bi 2o 3mass percent be 25% (be denoted as 75% BiOBr/Bi 2o 3).Be 86% to the degradation rate of methyl orange.
Embodiment 5
(1) bismuth oxide (Bi 2o 3) preparation: with embodiment 1.
(2) BiOBr/Bi 2o 3the preparation of compound: get 0.8 g Bi 2o 3be dissolved in 0.5 molL of 11.0 ml -1in HBr, vigorous stirring, makes it to dissolve completely; Afterwards, regulate pH to be 6 with diluted concentrated ammonia liquor, after stirring 15 minutes, 40 DEG C of stirring in water bath 0.5 h, after centrifugal, washing, drying, by the pulverulent solids obtained; Put into crucible, proceed to Muffle furnace 300 DEG C calcining 1 h, obtain BiOBr/Bi 2o 3compound.In compound, the mass percent of BiOBr is 65%, Bi 2o 3mass percent be 35% (be denoted as 65% BiOBr/Bi 2o 3), be 70% to the degradation rate of methyl orange.

Claims (5)

1. a BiOBr/Bi 2o 3the preparation method of hetero-junctions composite catalyst is by Bi 2o 3fully be dissolved in HBr solution, under stirring, make HBr at Bi 2o 3surface in situ hydrolysis BiOBr, forms the BiOBr/Bi that surface is stratiform 3D nanostructured 2o 3.
2. BiOBr/Bi as claimed in claim 1 2o 3the preparation method of hetero-junctions composite catalyst, is characterized in that: by Bi 2o 3be dissolved in HBr solution, regulate pH=4-8 with ammoniacal liquor, in 40 ~ 50 DEG C of stirring reaction 0.5 ~ 1 h, centrifugal, washing, after drying, high-temperature calcination, obtains BiOBr/Bi 2o 3hetero-junctions composite catalyst.
3. BiOBr/Bi as claimed in claim 1 or 2 2o 3the preparation method of hetero-junctions composite catalyst, is characterized in that: in above-mentioned HBr solution, and the concentration of HBr is 0.4 ~ 0.6 molL -1.
4. BiOBr/Bi as claimed in claim 1 or 2 2o 3the preparation method of hetero-junctions composite catalyst, is characterized in that: Bi 2o 3be 1:1.4 ~ 1:2 with the mol ratio of HBr.
5. BiOBr/Bi as claimed in claim 1 2o 3the preparation method of hetero-junctions composite catalyst, is characterized in that: above-mentioned high-temperature calcination calcines 1 ~ 4 h at 200 ~ 400 DEG C.
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CN105572176B (en) * 2016-02-25 2018-04-03 济南大学 A kind of preparation method and application of the toluene gas sensor based on base metal doped and compounded material
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CN108187699A (en) * 2018-01-31 2018-06-22 安徽师范大学 BiOX-Bi4O5X2Hetero-junctions and its preparation method and application
CN109847780A (en) * 2019-01-30 2019-06-07 太原理工大学 A kind of AgBr/BiOI/g-C3N4The preparation method and applications of tri compound catalysis material
CN110420650A (en) * 2019-07-26 2019-11-08 北京理工大学 A kind of preparation method of core-shell structure Bi/BiOBr composite material
CN112495403A (en) * 2020-12-14 2021-03-16 陕西科技大学 BiOCl/Bi2O3Photocatalytic material and preparation method and application thereof
CN112495403B (en) * 2020-12-14 2024-02-02 陕西科技大学 BiOCl/Bi 2 O 3 Photocatalytic material and preparation method and application thereof
CN115007208A (en) * 2022-07-08 2022-09-06 贵州民族大学 Preparation method and application of graphene/cellulose aerogel-based composite photocatalyst
CN115007208B (en) * 2022-07-08 2023-07-14 贵州民族大学 Preparation method and application of graphene/cellulose aerogel-based composite photocatalyst
CN116564717A (en) * 2023-04-28 2023-08-08 哈尔滨工业大学（深圳） Bi-based composite electrode material, preparation method and application thereof
CN116564717B (en) * 2023-04-28 2024-03-12 哈尔滨工业大学（深圳） Bi-based composite electrode material, preparation method and application thereof

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