CN104772134A - Method for massively preparing mesoporous BiVO4/Bi2O3 composite micro-rod p-n heterojunction photocatalyst - Google Patents

Method for massively preparing mesoporous BiVO4/Bi2O3 composite micro-rod p-n heterojunction photocatalyst Download PDF

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CN104772134A
CN104772134A CN201510148053.2A CN201510148053A CN104772134A CN 104772134 A CN104772134 A CN 104772134A CN 201510148053 A CN201510148053 A CN 201510148053A CN 104772134 A CN104772134 A CN 104772134A
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CN104772134B (en
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胡勇
毛梦梦
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Zhejiang Normal University CJNU
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Abstract

The invention relates to a method for massively preparing a mesoporous BiVO4/Bi2O3 composite micro-rod p-n heterojunction photocatalyst. The method for massively preparing the mesoporous BiVO4/Bi2O3 composite micro-rod p-n heterojunction photocatalyst takes metal inorganic salt-bismuth nitrate pentahydrate (Bi (NO3) 3.5H2O) as a reaction precursor, polyvinylpyrrolidone (PVP) as a surface active agent as well as sodium oxalate (Na2C2O4) and sodium metavanadate (NaVO3) as reactants; the method comprises the steps of feeding the surface active agent into the reaction precursor, carrying out a solvothermal reaction, centrifuging, washing, drying, and carrying out solid-phase reaction calcination on the obtained product at the temperature of 300-400 DEG C to obtain the BiVO4/Bi2O3 composite micro-rod p-n heterojunction photocatalyst. The prepared mesoporous BiVO4/Bi2O3 composite micro-rod p-n heterojunction photocatalyst has the length of about 3.5-4.5mu m, the diameter of about 0.7-0.9mu m and the mesoporous average diameter of 30.0nm. The prepared mesoporous BiVO4/Bi2O3 composite micro-rod p-n heterojunction photocatalyst has the characteristics of being low in cost, easy to control, good in repeatability, and the like.

Description

The mesoporous BiVO of a kind of a large amount of preparation 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound
Technical field
The invention belongs to mesoporous BiVO 4/ Bi 2o 3the micro-excellent preparing technical field of compound, particularly relates to a kind of mesoporous BiVO 4/ Bi 2o 3the chemical synthesis process of the solid phase reaction of the micro-film/nanorod p-n junction photochemical catalyst of compound.
Background technology
Pucherite (BiVO 4) as a kind of important semi-conducting material, because it is safe from harm to human body and environment, become inorganic material popular at present.BiVO 4chemical reaction can be promoted when the light contacting the sun and fluorescent lamp, it can kill multiple mushroom and virus etc., in acceleration chemical reaction process, does not cause the wasting of resources to be formed with additional pollution, this is the growth requirement meeting low-carbon economy, therefore BiVO 4have a wide range of applications in the field such as pigment and photocatalytic degradation.At present, bibliographical information prepares BiVO 4the method of nano material has: the multiple methods such as hydro-thermal method, microwave method, chemical deposition and high temperature solid state reaction.Solvent structure spindle build BiVO was reported in " physical chemistry magazine C " (2009,113 volumes 20228 pages) of American Chemical Society 4.Patent CN201310138022.X discloses solvent structure different-shape BiVO 4method.But a lot of method prepares single BiVO 4size is heterogeneity mostly, and cost of manufacture is relatively high, performance exists certain defect etc., and the nano material of therefore synthesizing hybrid structure has been called the focus of scientists study.
P-n junction photochemical catalyst is the photochemical catalyst be compounded to form by p-type semiconductor and n-type semiconductor, is a kind of specific function material with good chemical function, can be effectively separated light induced electron and hole.P-n junction photocatalyst material can not only expand the wave-length coverage of wide band gap semiconducter, and suppresses the compound of carrier by internal electric field, drastically increases the photocatalysis performance of material, is subject to extensive concern." JACS " (2013,135 volumes 10286 pages) as American Chemical Society report the method for water heat transfer MoS2/n-rGO p-n junction photochemical catalyst hydrogen manufacturing.Meanwhile, patent CN201410360916.8 also reports electrodeposition process and prepares Bi 2o 3/ BiPO 4the method of p-n junction photocatalysis film material.But a lot of method relates to the operation such as high temperature, low pressure, not only power consumption but also consuming time.Current synthesising mesoporous BiVO 4/ Bi 2o 3the micro-rod of compound realizes low cost simultaneously, easy to control, reproducible method is not also reported.The method of this patent introduction can not only control mesoporous BiVO easily 4/ Bi 2o 3the growth of the micro-rod of compound, and the production cost that effectively can reduce material, building-up process is simple, easy to control, and product yield is large, reproducible, and has excellent photo catalytic reduction performance.
Summary of the invention
The present invention is directed to mesoporous BiVO 4/ Bi 2o 3the micro-rod of compound is difficult to the problem of synthesizing, and provides a kind of low cost, the mesoporous BiVO of easy to control, reproducible preparation 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound.
Technical scheme of the present invention realizes in the following way: the mesoporous BiVO of a kind of a large amount of preparation 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound, with metal inorganic salt five water bismuth nitrate (Bi (NO 3) 35H 2o) be pre-reaction material, add surfactant polyvinylpyrrolidone (PVP), with sodium oxalate (Na 2c 2o 4) and sodium metavanadate (NaVO 3) be reactant, after solvent thermal reaction, through centrifugal, washing, dry, the product obtained is obtained mesoporous BiVO by 300 ~ 400 DEG C of solid phase reaction calcinings 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound.
Mesoporous BiVO is prepared in a large number in described one 4/ Bi 2o 3in the method for the micro-film/nanorod p-n junction photochemical catalyst of compound, prepare mesoporous BiVO 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound comprises following steps:
(1) get a certain amount of inorganic salts bismuth nitrate (Bi (NO 3) 35H 2o) and ethylene glycol (EG), Bi is made into 3+molar concentration is the solution of 0.01 ~ 0.035M, adds appropriate polyvinylpyrrolidone (PVP) and is dissolved in wherein, obtain colourless transparent solution A, solution A is put into container and at room temperature carries out magnetic agitation;
(2) get a certain amount of sodium oxalate (Na 2c 2o 4) and water, be made into the solution B that oxalate molar concentration is 0.016 ~ 0.04M, solution B dropwise added in solution A, solution becomes muddy gradually, treats that solution B all drips end, continues stirring 15 ~ 20 minutes, obtains mixed solution C;
(3) get a certain amount of sodium metavanadate (NaVO 3) and water, being mixed with metavanadic acid root molar concentration is the solution D of 0.002 ~ 0.007M, then solution D is dropwise added step (2) in the mixed solution C that obtains, turn yellow gradually through reaction, treat that solution D drips to terminate, continue stirring 15 ~ 20 minutes, obtain the mixed liquor E of yellow gum shape;
(4) be transferred in reactor by mixed liquor E, at 160 ~ 180 DEG C, react after 8 ~ 12 hours, centrifuge washing, oven dry, obtain mesoporous BiVO 4/ Bi 2o 3the micro-excellent presoma of compound;
By step (4) in the mesoporous BiVO that obtains 4/ Bi 2o 3the micro-excellent presoma of compound puts into tube furnace, calcines 3 ~ 5 hours, obtain mesoporous BiVO in 300 ~ 400 DEG C of air atmospheres 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound.
Adopt the mesoporous BiVO prepared by the present invention 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound, its length is about 3.5-4.5 μm, and diameter is about 0.7-0.9 μm, and mesoporous average diameter is 30.0nm.Mesoporous BiVO prepared by the present invention 4/ Bi 2o 3compound micro-film/nanorod p-n junction photochemical catalyst has the features such as product cost is low, easy to control, reproducible.
Accompanying drawing explanation
Fig. 1 is the mesoporous BiVO of preparation in the embodiment 1 surveyed of Dutch PHILIPS Co. PW3040/60 type x-ray diffractometer 4/ Bi 2o 3the x-ray diffraction pattern of the micro-film/nanorod p-n junction photochemical catalyst of compound, wherein: abscissa X is angle of diffraction (2 θ), and ordinate Y is relative diffracted intensity.
The mesoporous BiVO of preparation in embodiment 2 observed by Tu2Shi HIT S-4800 type field emission scanning electron microscope (FE-SEM) 4/ Bi 2o 3the shape appearance figure of the micro-film/nanorod p-n junction photochemical catalyst of compound.
The mesoporous BiVO of preparation in the embodiment 3 that Tu3Shi Jeol Ltd. JEM-2100F type transmission electron microscope (TEM) observes 4/ Bi 2o 3compound micro-film/nanorod p-n junction photochemical catalyst internal structure picture.
Mesoporous BiVO prepared by the embodiment 3 that Tu4Shi Jeol Ltd. JEM-2100F type high resolution transmission electron microscopy (HRTEM) observes 4/ Bi 2o 3biVO in the micro-film/nanorod p-n junction photochemical catalyst of compound 4and Bi 2o 3the lattice fringe picture corresponding to heterojunction structure formed.
The embodiment 4 intermediary hole BiVO that Tu5Shi Micromeritics Instrument Corp. U.S.A ASAP 2020 type physical adsorption appearance provides 4/ Bi 2o 3the adsorption isotherm of the micro-film/nanorod p-n junction photochemical catalyst of compound, illustration is its graph of pore diameter distribution.
Fig. 6 is embodiment 5 intermediary hole BiVO 4/ Bi 2o 3compound micro-film/nanorod p-n junction photochemical catalyst photocatalytically degradating organic dye methyl orange (MO) resolution chart.
Fig. 7 is mesoporous BiVO 4/ Bi 2o 3compound micro-film/nanorod p-n junction photochemical catalyst Mechanism of Semiconductor Photocatalytic Degradation figure.
Detailed description of the invention
Below by embodiment to preparing mesoporous BiVO in the present invention 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound is made and further being illustrated.
Embodiment 1
One prepares mesoporous BiVO 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound, this prepares mesoporous BiVO 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound comprises the following steps:
(1) take 0.1698g (0.35mmol) Bi (NO 3) 35H 2o, 0.5g (4.5mmol) PVP, is dissolved in 15ml ethylene glycol and forms Bi through ultrasonic disperse 3+molar concentration is the homogeneous solution A of 0.023M, solution A is poured into round-bottomed flask and at room temperature carries out magnetic agitation;
(2) take 0.0375g (0.28mmol) Na 2c 2o 4be dissolved in 10mL distilled water and obtain oxalate (C 2o 4 2-) molar concentration is the solution B of 0.028M, solution B dropwise joined in solution A, solution becomes muddy gradually, drips after terminating, stirs 15 ~ 20 minutes, obtain mixed solution C;
(3) take 0.0085g (0.07mmol) NaVO 3be dissolved in 15mL distilled water and obtain metavanadic acid root (VO 3 -) molar concentration is the solution D of 0.0047M, solution D is dropwise added step (2) in the mixed solution that obtains, turn yellow gradually through reaction, treat that solution D drips and terminate, stir 15 ~ 20 minutes, obtain the mixed liquor E of yellow gum shape;
(4) mixed liquor E is put into 50mL reactor, after 10 hours, respectively wash 3 time with distilled water and absolute ethyl alcohol through 180 DEG C of reactions, dry at 60 DEG C, obtain mesoporous BiVO 4/ Bi 2o 3the micro-excellent presoma of compound;
By step (4) in the mesoporous BiVO that obtains 4/ Bi 2o 3the micro-excellent presoma of compound is placed in tube furnace and calcines 4 hours in 350 DEG C under air atmosphere, obtains mesoporous BiVO 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound.
For the mesoporous BiVO prepared in the present embodiment 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound does X-ray diffraction analysis, and as shown in Figure 1, its abscissa X is angle of diffraction (2 θ) to result, and ordinate Y is relative diffracted intensity, BiVO in figure 4all diffraction maximums can change into (011) (121) (040) (200) etc. according to monoclinic system (monoclinic) index, with the JCPDS in international standard powder X-ray RD diffraction card, 14-0688 is consistent, Bi in figure 2o 3all diffraction maximums can change into (201) (220) (222) etc. according to tetragonal crystal system (tetragonal) index, and with the JCPDS in international standard powder X-ray RD diffraction card, 27-0050 is consistent.
Embodiment 2
One prepares mesoporous BiVO 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound, this prepares mesoporous BiVO 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound comprises the following steps:
(1) take 0.097g (0.2mmol) Bi (NO 3) 35H 2o, 0.5g (4.5mmol) PVP, is dissolved in 15ml ethylene glycol and forms Bi through ultrasonic disperse 3+molar concentration is the homogeneous solution A of 0.013M, solution A is poured into round-bottomed flask and at room temperature carries out magnetic agitation;
(2) take 0.0214g (0.16mmol) Na 2c 2o 4be dissolved in 10mL distilled water and obtain oxalate (C 2o 4 2-) molar concentration is the solution B of 0.016M, solution B dropwise joined in solution A, solution becomes muddy gradually, drips after terminating, stirs 15 ~ 20 minutes, obtain mixed solution C;
(3) take 0.0049g (0.04mmol) NaVO 3be dissolved in 15mL distilled water and obtain metavanadic acid root (VO 3 -) molar concentration is the solution D of 0.0027M, solution D is dropwise added step (2) in the mixed solution that obtains, turn yellow gradually through reaction, treat that solution D drips and terminate, stir 15 ~ 20 minutes, obtain the mixed liquor E of yellow gum shape;
(4) mixed liquor E is put into 50mL reactor, after 10 hours, respectively wash 3 time with distilled water and absolute ethyl alcohol through 170 DEG C of reactions, dry at 60 DEG C, obtain mesoporous BiVO 4/ Bi 2o 3the micro-excellent presoma of compound;
By step (4) in the mesoporous BiVO that obtains 4/ Bi 2o 3the micro-excellent presoma of compound is placed in tube furnace and calcines 5 hours in 350 DEG C under air atmosphere, obtains mesoporous BiVO 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound.
For the mesoporous BiVO prepared in the present embodiment 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound does field emission scanning electron microscope analysis, and as shown in Figure 2, can find out that product is that porous is bar-shaped, length is at about 3.5-4.5 μm, and diameter is at about 0.7-0.9 μm for the electromicroscopic photograph obtained.
Embodiment 3
One prepares mesoporous BiVO 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound, this prepares mesoporous BiVO 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound comprises the following steps:
(1) take 0.194g (0.4mmol) Bi (NO 3) 35H 2o, 0.5g (4.5mmol) PVP, is dissolved in 15ml ethylene glycol and forms Bi through ultrasonic disperse 3+molar concentration is the homogeneous solution A of 0.027M, solution A is poured into round-bottomed flask and at room temperature carries out magnetic agitation;
(2) take 0.0429g (0.32mmol) Na 2c 2o 4be dissolved in 10mL distilled water and obtain oxalate (C 2o 4 2-) molar concentration is the solution B of 0.032M, solution B dropwise joined in solution A, solution becomes muddy gradually, drips after terminating, stirs 15 ~ 20 minutes, obtain mixed solution C;
(3) take 0.0098g (0.08mmol) NaVO 3be dissolved in 15mL distilled water and obtain metavanadic acid root (VO 3 -) molar concentration is the solution D of 0.0053M, solution D is dropwise added step (2) in the mixed solution that obtains, turn yellow gradually through reaction, treat that solution D drips and terminate, stir 15 ~ 20 minutes, obtain the mixed liquor E of yellow gum shape;
(4) mixed liquor E is put into 50mL reactor, after 8 hours, respectively wash 3 time with distilled water and absolute ethyl alcohol through 180 DEG C of reactions, dry at 60 DEG C, obtain mesoporous BiVO 4/ Bi 2o 3the micro-excellent presoma of compound;
By step (4) in the mesoporous BiVO that obtains 4/ Bi 2o 3the micro-excellent presoma of compound is placed in tube furnace and calcines 4 hours in 300 DEG C under air atmosphere, obtains mesoporous BiVO 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound.
For the present embodiment intermediary hole BiVO 4/ Bi 2o 3the micro-rod of compound does tem study.As can be seen from Figure 3, the BiVO for preparing of the present embodiment 4/ Bi 2o 3the micro-excellent surface of compound has pore space structure.
For the present embodiment intermediary hole BiVO 4/ Bi 2o 3the micro-rod of compound does high resolution transmission electron microscopy analysis.As can be seen from Figure 4, BiVO 4/ Bi 2o 3the lattice fringe corresponding to heterojunction structure formed in the micro-rod of compound is respectively BiVO 4and Bi 2o 3lattice fringe picture.
Embodiment 4
One prepares mesoporous BiVO 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound, this prepares mesoporous BiVO 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound comprises the following steps:
(1) take 0.22g (0.5mmol) Bi (NO 3) 35H 2o, 0.5g (4.5mmol) PVP, is dissolved in 15ml ethylene glycol and forms Bi through ultrasonic disperse 3+molar concentration is the homogeneous solution A of 0.033M, solution A is poured into round-bottomed flask and at room temperature carries out magnetic agitation;
(2) take 0.0536g (0.4mmol) Na 2c 2o 4be dissolved in 10mL distilled water and obtain oxalate (C 2o 4 2-) molar concentration is the solution B of 0.04M, solution B dropwise joined in solution A, solution becomes muddy gradually, drips after terminating, stirs 15 ~ 20 minutes, obtain mixed solution C;
(3) take 0.0122g (0.1mmol) NaVO 3be dissolved in 15mL distilled water and obtain metavanadic acid root (VO 3 -) molar concentration is the solution D of 0.0067M, solution D is dropwise added step (2) in the mixed solution that obtains, turn yellow gradually through reaction, treat that solution D drips and terminate, stir 15 ~ 20 minutes, obtain the mixed liquor E of yellow gum shape;
(4) mixed liquor E is put into 50mL reactor, after 12 hours, respectively wash 3 time with distilled water and absolute ethyl alcohol through 180 DEG C of reactions, dry at 60 DEG C, obtain mesoporous BiVO 4/ Bi 2o 3the micro-excellent presoma of compound;
By step (4) in the mesoporous BiVO that obtains 4/ Bi 2o 3the micro-excellent presoma of compound is placed in tube furnace and calcines 3 hours in 350 DEG C under air atmosphere, obtains mesoporous BiVO 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound.
For the mesoporous BiVO prepared in the present embodiment 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound is N 2adsorption desorption is tested, and as shown in Figure 5, the absorption isotherm of sample belongs to IV type and has H3 hysteresis loop the information obtained, and these can prove that this sample is mesoporous material further.Graph of pore diameter distribution in illustration more intuitively reality goes out the pore-size distribution of sample, and bore dia is about 30.0nm.
Embodiment 5
One prepares mesoporous BiVO 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound, this prepares mesoporous BiVO 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound comprises the following steps:
(1) take 0.1698g (0.35mmol) Bi (NO 3) 35H 2o, 0.5g (4.5mmol) PVP, is dissolved in 15ml ethylene glycol and forms Bi through ultrasonic disperse 3+molar concentration is the homogeneous solution A of 0.023M, solution A is poured into round-bottomed flask and at room temperature carries out magnetic agitation;
(2) take 0.0375g (0.28mmol) Na 2c 2o 4be dissolved in 10mL distilled water and obtain oxalate (C 2o 4 2-) molar concentration is the solution B of 0.028M, solution B dropwise joined in solution A, solution becomes muddy gradually, drips after terminating, stirs 15 ~ 20 minutes, obtain mixed solution C;
(3) take 0.0085g (0.07mmol) NaVO 3be dissolved in 15mL distilled water and obtain metavanadic acid root (VO 3 -) molar concentration is the solution D of 0.0047M, solution D is dropwise added step (2) in the mixed solution that obtains, turn yellow gradually through reaction, treat that solution D drips and terminate, stir 15 ~ 20 minutes, obtain the mixed liquor E of yellow gum shape;
(4) mixed liquor E is put into 50mL reactor, after 10 hours, respectively wash 3 time with distilled water and absolute ethyl alcohol through 160 DEG C of reactions, dry at 60 DEG C, obtain mesoporous BiVO 4/ Bi 2o 3the micro-excellent presoma of compound;
By step (4) in the mesoporous BiVO that obtains 4/ Bi 2o 3the micro-excellent presoma of compound is placed in tube furnace and calcines 4 hours in 400 DEG C under air atmosphere, obtains mesoporous BiVO 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound.
To the mesoporous BiVO prepared in the present embodiment 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound and business BiVO 4do the test of photocatalytically degradating organic dye methyl orange (MO) performance comparison, the test result obtained as shown in Figure 6, can be found out when 30min, business BiVO 4degradation rate be 12.4%, and mesoporous BiVO 4/ Bi 2o 3compound micro-film/nanorod p-n junction photocatalyst for degrading speed is 70.9%, and this shows mesoporous BiVO 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound can more effectively be degraded MO at short notice.Prepared BiVO 4/ Bi 2o 3composite not only has meso pore characteristics and effectively improves photocatalysis efficiency, the p-n heterojunction structure that it is formed as shown in Figure 7, BiVO 4for n-type semiconductor, Bi 2o 3for p-type semiconductor, both all can be excited under visible light, when both fermi levels reach balance, will p-n junction be formed, and due to electrons spread, form an internal electric field at its contact interface, this electric field inhibits the compound in light induced electron and hole, thus improves photocatalysis performance.
The result that XRD, FE-SEM, TEM, HRTEM, pore structure and absorption property are measured and photocatalytically degradating organic dye performance test show:
Adopt the preparation-obtained mesoporous BiVO of the inventive method 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound is the catalysis material successfully synthesized by current better simply one-step method, and it has, and cost is low, output is high, appearance and size uniformity is good, reappearance high, and it has been filled up solvent-thermal method and has prepared mesoporous BiVO 4/ Bi 2o 3the blank of the micro-film/nanorod p-n junction photocatalyst compound material of compound in synthesis field, for synthesising mesoporous BiVO 4/ Bi 2o 3compound micro-film/nanorod p-n junction photocatalyst material is developed further, is applied and can play certain impetus.

Claims (2)

1. prepare mesoporous BiVO in a large number for one kind 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound, is characterized in that with metal inorganic salt five water bismuth nitrate (Bi (NO 3) 35H 2o) be pre-reaction material, add surfactant polyvinylpyrrolidone (PVP), with sodium oxalate (Na 2c 2o 4) and sodium metavanadate (NaVO 3) be reactant, after solvent thermal reaction, through centrifugal, washing, dry, the product obtained is obtained mesoporous BiVO by 300 ~ 400 DEG C of solid phase reaction calcinings 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound.
2. one according to claim 1 prepares mesoporous BiVO in a large number 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound, is characterized in that this mesoporous BiVO of preparation in a large number 4/ Bi 2o 3the method of the micro-film/nanorod p-n junction photochemical catalyst of compound comprises the following steps:
(1) get a certain amount of inorganic salts bismuth nitrate (Bi (NO 3) 35H 2o) and ethylene glycol (EG), Bi is made into 3+molar concentration is the solution of 0.01 ~ 0.035M, adds appropriate polyvinylpyrrolidone (PVP) and is dissolved in wherein, obtain colourless transparent solution A, solution A is put into container and at room temperature carries out magnetic agitation;
(2) get a certain amount of sodium oxalate (Na 2c 2o 4) and water, be made into the solution B that oxalate molar concentration is 0.016 ~ 0.04M, solution B dropwise added in solution A, solution becomes muddy gradually, treats that solution B all drips end, continues stirring 15 ~ 20 minutes, obtains mixed solution C;
(3) get a certain amount of sodium metavanadate (NaVO 3) and water, being mixed with metavanadic acid root molar concentration is the solution D of 0.002 ~ 0.007M, then solution D is dropwise added step (2) in the mixed solution C that obtains, turn yellow gradually through reaction, treat that solution D drips to terminate, continue stirring 15 ~ 20 minutes, obtain the mixed liquor E of yellow gum shape;
(4) be transferred in reactor by mixed liquor E, at 160 ~ 180 DEG C, react after 8 ~ 12 hours, centrifuge washing, oven dry, obtain mesoporous BiVO 4/ Bi 2o 3the micro-excellent presoma of compound;
By step (4) in the mesoporous BiVO that obtains 4/ Bi 2o 3the micro-excellent presoma of compound puts into tube furnace, calcines 3 ~ 5 hours, obtain mesoporous BiVO in 300 ~ 400 DEG C of air atmospheres 4/ Bi 2o 3the micro-film/nanorod p-n junction photochemical catalyst of compound.
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