CN103285885B - CdS-intercalated and Mn-doped K4Nb6O17 composite photocatalytic material and preparation method thereof - Google Patents

CdS-intercalated and Mn-doped K4Nb6O17 composite photocatalytic material and preparation method thereof Download PDF

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CN103285885B
CN103285885B CN201210596465.9A CN201210596465A CN103285885B CN 103285885 B CN103285885 B CN 103285885B CN 201210596465 A CN201210596465 A CN 201210596465A CN 103285885 B CN103285885 B CN 103285885B
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cds
doping
intercalation
composite photocatalyst
photocatalyst material
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CN103285885A (en
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梁英华
崔文权
刘利
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Hebei United University
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Hebei United University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention belongs to the technical field of photocatalysis and relates to a CdS-intercalated and Mn-doped K4Nb6O17 composite photocatalytic material and a preparation method thereof, which solve the problem of low visible-light utilization rate of a traditional photocatalyst. The catalyst material disclosed by the invention is prepared by intercalating CdS into Mn-doped K4Nb6O17 board layers; the Mn-doped K4Nb6O17 is prepared by adopting a high-temperature solid-phase method, and by an interlayer ion exchange action, an amine intercalation reaction and a sulfuration action, the CdS-intercalated and Mn-doped K4Nb6O17 composite photocatalytic material is prepared and is used for degrading organic pollutants by photocatalysis; and compared with an existing laminated compound photocatalytic material, the CdS-intercalated and Mn-doped K4Nb6O17 composite photocatalytic material has the advantage that the catalytic activity is obviously improved under the visible light.

Description

A kind of CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material and preparation method thereof
Technical field
The present invention relates to a kind of CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material and preparation method thereof, belongs to photocatalysis technology field, can be used for the preparation of green novel energy source hydrogen or the catalytic degradation of pollutant.
Background technology
Energy and environment problem is two hang-ups that the mankind face for a long time, on the one hand, earth non-renewable resources are along with the use of accumulating over a long period, approach exhaustion, according to interrelated data display, the Expenditure Levels of the global coal resources more with current earth storage capacity, is also about to exhausted less than the times of 200 years, oil can only maintain the time less than 100 years especially, develops renewable green alternate resources extremely urgent; On the other hand, along with the fast development of industry, a large amount of discharges of various discarded object, severe contamination natural environment, threatens the sustainable development of human society, and control of environmental pollution problem is very urgent.Last century the seventies, the people such as A.Fujishima and K.Honda are first with TiO 2for in the photoelectrochemical cell of positive electrode, find the photocatalysis Decomposition effect of water, opened new era of photocatalysis field.In the last few years, Japan, the research of conductor photocatalysis hydrogen manufacturing had been risen gradually in the states such as the U.S., and how to produce at catalyst, and the aspects such as catalyst modification achieve certain progress.Recently, semiconductor light-catalyst purification also achieves with decomposing organic pollutant aspect and applies widely.
Photocatalitic Technique of Semiconductor refers to the irradiation utilizing light to semiconductor, makes electronics produce valence band to the transition of conduction band, conduction band produces light induced electron, valence band produces hole.Wherein, light induced electron can by the H in water +be reduced to hydrogen, organic matter degradation can be CO by hole 2and H 2the inorganic molecules such as O.Preparing highly active photochemical catalyst is the key issue improving photocatalysis hydrogen production efficiency.Layered semiconductor photochemical catalyst itself has hydrogen and generates activated centre, water just can be made to resolve into H without the need to supporting the noble metals such as Pt 2and O 2, be study many class photochemical catalyst, wherein K 4nb 6o 17it is most typical lamellar compound.K 4nb 6o 17nbO 6the two-dimensional layer compound that octahedra unit connects and composes through bridging oxygen.But, K 4nb 6o 17energy gap is about 3.2 eV, the same with most of lamellar compound, cannot absorb visible ray.
Ion doping and low energy gap molecule intercalation are two kinds and change photochemical catalyst energy gap, improve the important method of its visible ray utilization rate.Foreign aid's ion is mixed K 4nb 6o 17in lattice, be equivalent at K 4nb 6o 17conduction band and valence band between insert new conduction level, form new activated centre, change K 4nb 6o 17band structure, reduces its energy gap, expands K 4nb 6o 17to can by the response of light.By low energy gap molecule intercalation K 4nb 6o 17, utilize the sensibilization of low energy gap molecule to improve the visible light-responded scope of potassium niobate, and suppress photo-generate electron-hole compound, improve photocatalytic activity.But single modified K 4nb 6o 17visible light catalysis activity is still unsatisfactory, constrains its practical application and popularization.Therefore, combine ion doping and intercalation synthesis two kinds of methods common modified photocatalytic material, is the new approach improving catalysis material.
At present about CdS intercalation Mn doping K 4nb 6o 17the preparations and applicatio of composite photocatalyst material there is not yet relevant report.
Summary of the invention
The object of the invention is the deficiency overcoming existing photocatalysis technology, propose a kind of CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material and preparation method thereof, is intended to the utilization rate and the photocatalysis efficiency that improve visible ray.
Content of the present invention is a kind of CdS intercalation Mn doping K 4nb 6o 17the preparation method of composite photocatalyst material and Photocatalytic Performance Study thereof, the technical scheme taked is:
a kind of CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material, this composite photocatalyst material structure: Mn ion substitution Nb ion enters lamellar compound K 4nb 6o 17in sites, nanoscale CdS molecule inserts K simultaneously 4nb 6o 17between flaggy, form a kind of nanoscale CdS intercalation Mn ion doping K 4nb 6o 17compound catalysis material.Nb/Mn atomic molar is 10:1 ~ 10:4 than the mol ratio for 100:1 ~ 39:1, Mn+Nb and Cd, and the preparation of this catalyst comprises the following steps, and adopts high temperature solid-state method to prepare Mn doping K 4nb 6o 17body, and then adopt acid exchange, ion-exchange, vulcanisation step to prepare CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material.
CdS intercalation Mn adulterates K 4nb 6o 17the preparation method of composite photocatalyst material refers to and takes Nb by amount of substance than 3:2 2o 5, K 2cO 3, Nb/Mn mol ratio is that 100:1 ~ 39:1 takes MnO in addition 2, with Nb 2o 5, K 2cO 3be ground, high temperature solid state reaction 2 ~ 6 h at 800 ~ 1000 DEG C, after being cooled to room temperature, sample be first placed on the C of 0.5 ~ 1.5 mol/L hydrochloric acid, 20 ~ 80 % percents by volume 4h 9nH 2cd (the CH of solution, 0.3 ~ 0.5 mol/L 3cOO) 2in solution, stir 1 ~ 72 h continuously under 25 ~ 90 DEG C of water-baths or microwave irradiation condition, after product separation drying, will H be placed in 2sulfuration in S gaseous environment, namely obtains CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material (K 4nb 6-xmn xo 17/ CdS).
preferablythe preparation method of this composite photocatalyst material, comprises the following steps:
Step one takes Nb by amount of substance than 3:2 2o 5, K 2cO 3(preferred K 2cO 3separately excessive 10% to compensate the loss of alkali-metal vaporization at high temperature), Nb/Mn mol ratio is that 100:1 ~ 39:1 takes MnO in addition 2, with Nb 2o 5, K 2cO 3be ground, high temperature solid state reaction 2 ~ 6 h at 800 ~ 1000 DEG C, after being cooled to room temperature, take out (being preferably ground to powdery), obtain Mn doping K 4nb 6o 17composite catalyst (K 4nb 6-xmn xo 17).
The doped samples that step one obtains by step 2 is placed in 0.5 ~ 1.5 mol/L hydrochloric acid, stirs 1 ~ 72 h continuously under 25 ~ 90 DEG C of water-baths or microwave irradiation condition, and dry after product centrifugation (preferably 50 ~ 110 DEG C of dryings 8 ~ 20 h).
The product that step 2 obtains by step 3 is placed in the C of 20 ~ 80 % percents by volume 4h 9nH 2in the aqueous solution, stir 1 ~ 72 h continuously under 25 ~ 90 DEG C of water-baths or microwave irradiation condition, dry after product centrifugation (preferably 50 ~ 110 DEG C of dryings 8 ~ 20 h).
The product that step 3 obtains by step 4 is placed in the Cd (CH of 0.3 ~ 0.5 mol/L 3cOO) 2in the aqueous solution, stir 1 ~ 72 h continuously under 25 ~ 90 DEG C of water-baths or microwave irradiation condition, dry after product centrifugation (preferably 50 ~ 110 DEG C of dryings 8 ~ 20 h).
The product that step 4 obtains by step 5 is placed in H 2sulfuration in S gaseous environment (preferably after sample all turns yellow), takes out sample, namely obtains CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material (K 4nb 6-xmn xo 17/ CdS).
The CdS intercalation Mn doping K that step 5 obtains 4nb 6o 17composite photocatalyst material, both can be applicable to photocatalysis degradation organic contaminant, can be used for again decomposition water (preferably can add hole sacrifice agent) hydrogen manufacturing.
Accompanying drawing explanation
Fig. 1 is the powder X-ray diffractogram (XRD) of different materials of the present invention.a：K 4Nb 6O 17；b：K 4Nb 5.85Mn 0.15O 17；c：K 4Nb 5.85Mn 0.15O 17/CdS。
Fig. 2 is CdS intercalation Mn of the present invention doping K 4nb 6o 17photocatalyzed Hydrogen Production figure under composite photocatalyst material visible ray.
Fig. 3 is CdS intercalation Mn of the present invention doping K 4nb 6o 17to the photocatalytic degradation figure of rhodamine B under composite photocatalyst material visible ray.
Detailed description of the invention
Catalyst preparing and the using method of the present invention's proposition is further described below by examples of implementation.
embodiment 1
Take Nb 2o 5, K 2cO 3, be that 10:0.1 takes MnO by Nb/Mn mol ratio in addition 2, with Nb 2o 5, K 2cO 3be ground, at 800 ~ 1000 DEG C, high temperature solid state reaction 2 ~ 6 h, takes out after being cooled to room temperature, is ground to powdery, obtains Mn doping K 4nb 6o 17composite catalyst (K 4nb 6-xmn xo 17).The doped samples obtained is placed in 1 mol/L hydrochloric acid, under 80 DEG C of microwave irradiation conditions, stirs 5 h, 110 DEG C of drying 10 h after product centrifugation continuously.Product is placed in the C of 50 % percents by volume 4h 9nH 2in the aqueous solution, under 80 DEG C of microwave irradiation conditions, stir 6 h, 60 DEG C of drying 5 h after product centrifugation continuously.The product obtained is placed in the Cd (CH of 0.5 mol/L 3cOO) 2in the aqueous solution, under 80 DEG C of microwave irradiation conditions, stir 6 h, 110 DEG C of drying 10 h after product centrifugation continuously.Product is placed in H 2sulfuration in S gaseous environment, after sample all turns yellow, takes out sample, namely obtains CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material.
embodiment 2
Get 0.5 gram of sample, with 250 ml 0.1mol/L Na 2s, 0.5 mol/L Na 2sO 3, the 1 mol/L KOH aqueous solution fully mixes in reative cell, and (visible ray passes into 1 mol/L NaNO to 1000 W xenon lamps in chuck 2solution as cooling medium and filter out xenon lamp produce a small amount of ultraviolet) irradiate under react 3h.a：K 4Nb 6O 17；b：K 4Nb 5.85Mn 0.15O 17；c：K 4Nb 6O 17/CdS；d：K 4Nb 5.85Mn 0.15O 17/CdS。As seen from the figure, CdS intercalation Mn doping K 4nb 6o 17photocatalyzed Hydrogen Production amount under composite photocatalyst material visible ray is 8.55 mmol/ (g cat), far above K 4nb 6o 17body, Mn adulterates K 4nb 6o 17compound catalyze material and CdS intercalation K 4nb 6o 17composite photocatalyst material.
embodiment 3
Get 0.5g sample and put into photochemical reaction instrument with 0.01 g/L rhodamine B solution respectively, after adsorbing half an hour, with the xenon lamp of 1000 W for light source, add optical filter between light source and rhodamine B solution, isolated ultraviolet light, carries out visible light photocatalysis reaction.React 2 h, every 15 min extract 3ml solution, and detectable concentration changes.As seen from the figure, CdS intercalation Mn doping K 4nb 6o 17be 94.38% to the catalysis degradation modulus of rhodamine B under composite photocatalyst material visible ray, effect is much better than K 4nb 6o 17body, Mn adulterates K 4nb 6o 17compound catalyze material and CdS intercalation K 4nb 6o 17composite photocatalyst material.

Claims (3)

1. a CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material, is characterized in that:
This composite photocatalyst material structure: Mn ionic portions replaces Nb ion and enters lamellar compound K 4nb 6o 17in sites, nanoscale CdS molecule inserts K simultaneously 4nb 6o 17between flaggy, form a kind of nanoscale CdS intercalation Mn doping K 4nb 6o 17compound catalysis material, Nb/Mn atomic molar is than being 10:1 ~ 10:4 for the mol ratio of 100:1 ~ 39:1, Mn+Nb and Cd, and the preparation of this catalyst comprises the following steps, and adopts high temperature solid-state method to prepare Mn doping K 4nb 6o 17body, and then adopt acid exchange, ion-exchange, vulcanisation step to prepare CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material.
2. CdS intercalation Mn doping K as described in claim 1 4nb 6o 17the preparation method of composite photocatalyst material, the method refers to and takes Nb by amount of substance than 3:2 2o 5, K 2cO 3, Nb/Mn mol ratio is that 100:1 ~ 39:1 takes MnO in addition 2, with Nb 2o 5, K 2cO 3be ground, high temperature solid state reaction 2 ~ 6 h at 800 ~ 1000 DEG C, after being cooled to room temperature, sample be first placed on the C of 0.5 ~ 1.5 mol/L hydrochloric acid, 20 ~ 80 % percents by volume 4h 9nH 2cd (the CH of solution, 0.3 ~ 0.5 mol/L 3cOO) 2in solution, stir 1 ~ 72 h continuously under 25 ~ 90 DEG C of water-baths or microwave irradiation condition, after product separation drying, will H be placed in 2sulfuration in S gaseous environment, namely obtains CdS intercalation Mn doping K 4nb 6o 17composite photocatalyst material (K 4nb 6-xmn xo 17/ CdS).
3. CdS intercalation Mn doping K as described in claim 1 4nb 6o 17composite photocatalyst material, is characterized in that both can be applicable to photocatalysis degradation organic contaminant, can be used for hydrogen production by water decomposition again.
CN201210596465.9A 2012-12-26 2012-12-26 CdS-intercalated and Mn-doped K4Nb6O17 composite photocatalytic material and preparation method thereof Expired - Fee Related CN103285885B (en)

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CN1513040A (en) * 2001-04-25 2004-07-14 南欧派克有限公司 Photocatalytic coating material having photocatalytic activity and adsorption property and method for preparating same

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Microwave-assisted synthesis of CdS intercalated K4Nb6O17 and its photocatalytic;Wenquan Cui等;《Applied Catalysis A: General》;20120229;第417-418卷;第111-118页 *
Ni、Co、Mn、Cu掺杂对K4 Nb6O17光催化活性的影响;杨亚辉等;《材料导报》;20050531;第19卷(第5期);第117-119页 *

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