CN117680168A - Lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology, and preparation method and application thereof - Google Patents
Lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology, and preparation method and application thereof Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 42
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 49
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 28
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- -1 halogen salt Chemical class 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000001621 bismuth Chemical class 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 27
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 3
- 230000029219 regulation of pH Effects 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 239000002154 agricultural waste Substances 0.000 abstract description 2
- 230000009849 deactivation Effects 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 29
- 238000003756 stirring Methods 0.000 description 24
- 239000011259 mixed solution Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000007789 sealing Methods 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 7
- 239000007833 carbon precursor Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 230000004298 light response Effects 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- 230000004083 survival effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-shaped morphology, a preparation method and application thereof, which utilizes lignin carbon induction and pH regulation with rich oxygen functional groups to synthesize the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material BiOX/C with the regular flower-shaped morphology, and the material has the advantages of wide spectral response range, high efficiency, strong stability, and the like, and the separation of photo-generated carriers and cavities is effectively promoted based on the flower-shaped morphology structure and the Z-type heterojunction of the material, so that the material has higher photo-reaction efficiency, and the defects of low quantum efficiency, slow degradation rate, poor stability, easy deactivation and the like of the traditional photocatalytic degradation organic pollutant material are effectively solved. The lignin carbon substrate material takes lignocellulose in agricultural wastes as a carbon source, is environment-friendly, low in production cost, simple and feasible in synthesis method, considerable in yield, mild in reaction condition in the photocatalytic degradation process of organic pollutants, simple and feasible in operation, and wide in application prospect.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-shaped morphology, and a preparation method and application thereof.
Background
In recent years, resource shortage and environmental pollution become more and more critical problems threatening future survival and development of human beings, and new phenomena, new theories and new technologies capable of degrading various pollutants safely, rapidly, with low energy consumption and high efficiency are developed and utilized to become hot spots continuously explored by vast scientific researchers. Due to the advantages of green, mild, energy saving and the like, in recent years, solar energy is used as the only energy source to drive the removal of pollutants in water, and the method gradually becomes one of the strategies for relieving the shortage of energy and protecting the water environment. The development of high-efficiency, environment-friendly, high-stability and low-cost light response materials, which are key steps for realizing high-efficiency water purification, also become the focus of attention of current and future scientists.
The mechanism of the photocatalytic degradation of the semiconductor to treat the organic pollution is to utilize the strong oxidizing property of holes orSome active species generated by electrons and holes in water, such as hydroxyl radicals (OH) and superoxide radicals (O) 2- ) And secondary free radicals thereof, which can perform a series of reactions such as addition, substitution, electron transfer and the like with organic pollutants in the system, and finally convert the organic pollutants into CO by breaking chemical bonds such as C-C bonds, C-H bonds and the like existing in the organic matters 2 And H 2 O realizes organic pollutant degradation. With TiO 2 Typical conventional semiconductor photocatalysts have a series of advantages of high stability, no toxicity, low cost, etc., but have a relatively wide band gap (e.g., anatase TiO 2 And rutile phase TiO 2 3.2eV and 3.0eV, respectively), only a relatively small amount of uv light can be utilized, limiting its practical application. In addition, the defects of easy recombination of photo-generated electrons and holes, easy agglomeration of nano particles and the like of the nano titanium dioxide are also greatly reduced 2 Is a component of the photocatalytic activity of the catalyst. Therefore, the development of the photocatalytic material with wide spectral response and high catalytic activity is very practical.
In recent years, a series of novel semiconductor photocatalytic materials have been developed to address these problems, including metal oxides (Ag 2 O、ZnO、SnO 2 、ZrO 2 ) Vanadate (BiAlVO) 7 、BiVO 4 ) Tungsten molybdate (Bi) 2 MoO 6 、Bi 2 WO 6 ) Bismuth oxyhalide (BiOCl, biOBr, biOI) and the like. Wherein bismuth oxyhalide BiOX (X=Cl, br and I) consisting of the main group V-VI-VII multicomponent has a structure consisting of [ Bi ] 2 O 2 ] 2+ The bond and halogen are interlaced and combined in a layered structure, so that the BiOX crystal forms a layer perpendicular to [ Bi ] 2 O 2 ] 2+ And halogen, can promote the separation of photo-generated electrons and holes, and the BiOX semiconductor has excellent photocatalytic activity. In addition, the band gap of the BiOX semiconductor is reduced from 4.18eV (BiOF) to 1.7eV (BiOI) along with the increase of the atomic number, so that the photocatalytic activity range of the material is greatly expanded, and the material has wide application prospect in the field of degrading organic pollutants. However, biOX materials have a plurality of problems, and BiOCl has no visible light response basically, so that the utilization of sunlight is limited; energy of BiOBrThe band width is proper, but the absorption range of visible light is narrow, and the energy band structure needs to be further regulated; the BiOI has narrower forbidden bandwidth, the photo-generated carriers and holes are easy to recombine, and the photo-catalytic efficiency is lower.
Disclosure of Invention
The invention aims to solve the technical problem of low photocatalytic efficiency of BiOX materials in the prior art, and provides a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-shaped morphology, and a preparation method and application thereof.
The invention solves the technical problems, and adopts the following technical scheme: the preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with the regular flower-shaped morphology comprises the following steps:
s1, dissolving a template agent and lignin in ethylene glycol together, carrying out ultrasonic dispersion and mixing, and then heating and evaporating to dryness to obtain a raw material A;
s2, heating the raw material A to 500-1000 ℃ at a heating rate of 1-5 ℃/min under the protection of nitrogen flow, and roasting for 6-12h to obtain a precursor B;
s3, adding the precursor B into a strong alkaline solution for heating reaction, and washing and drying after the reaction is finished to obtain lignin carbon;
s4, dropwise adding the aqueous solution of the halogen salt into the aqueous solution of the bismuth salt and the lignin carbon at the speed of 1-10 drops/second, uniformly mixing, regulating the pH value to 3-7, heating to 150-200 ℃ for reaction, centrifuging, washing, drying and grinding after the reaction is finished, and obtaining the lignin carbon-based bismuth oxyhalide composite material with regular flower-shaped morphology.
As the preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with the regular flower-shaped morphology, the preparation method is further optimized: the template agent in the step S1 is silica microspheres, and lignin is alkali lignin.
As the preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with the regular flower-shaped morphology, the preparation method is further optimized: the mass ratio of the silica microspheres to the alkali lignin is 1:1-1:10.
As the preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with the regular flower-shaped morphology, the preparation method is further optimized: the halogen salt in the step S4 is a mixture of two of potassium chloride, potassium bromide and potassium iodide.
As the preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with the regular flower-shaped morphology, the preparation method is further optimized: the molar ratio of the two halogen salts is 1:1-10:1.
As the preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with the regular flower-shaped morphology, the preparation method is further optimized: in the step S3, the strong alkaline solution is sodium hydroxide solution, and the heating reaction temperature is 80 ℃.
As the preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with the regular flower-shaped morphology, the preparation method is further optimized: in the step S4, ammonia water is used for adjusting the pH value of the solution.
The invention also provides a lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-shaped morphology, and the material is prepared by the method.
The invention also provides application of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with the regular flower-shaped morphology in a system for degrading organic pollutants by photocatalysis.
The invention has the following beneficial effects: aiming at the defects of the existing bismuth halide material, the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material BiOX/C with a wide spectral response range, high efficiency and strong stability and regular flower-shaped morphology is synthesized by utilizing lignin carbon induction and pH regulation with rich oxygen-containing functional groups, and the separation of photo-generated carriers and cavities is effectively promoted based on the flower-shaped morphology structure and the Z-shaped heterojunction of the material, so that the material has higher photo-reaction efficiency, and the defects of low quantum efficiency, slow degradation rate, poor stability, easiness in deactivation and the like of the traditional photocatalytic degradation organic pollutant material are effectively solved. The lignin carbon substrate material takes lignocellulose in agricultural wastes as a carbon source, is environment-friendly, low in production cost, simple and feasible in synthesis method, considerable in yield, mild in reaction condition in the photocatalytic degradation process of organic pollutants, simple and feasible in operation, and wide in application prospect.
Drawings
FIG. 1 shows BiOCl@C, biOCl x Br y SEM topography of @ C;
FIGS. 2 (a) and (b) are XRD patterns of BiOCl and BiOCl@C before and after the photocatalytic reaction, respectively;
FIG. 3 is PC, biOCl@C and BiOCl, respectively x Br y Ultraviolet-visible diffuse reflectance spectra at @ C;
FIG. 4 is BiOCl, biOCl@C and BiOBr x Cl y Performance graph of photocatalytic degradation of organic dye at @.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate, but are not to be construed as limiting the invention.
The preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with the regular flower-shaped morphology comprises the following steps:
s1, dissolving a template agent and lignin in ethylene glycol together, carrying out ultrasonic dispersion and mixing, and then heating and evaporating to dryness to obtain a raw material A.
The template agent can be silicon dioxide microspheres, the lignin is alkali lignin, and the mass ratio of the silicon dioxide microspheres to the alkali lignin is 1:1-1:10.
S2, heating the raw material A to 500-1000 ℃ at a heating rate of 1-5 ℃/min under the protection of nitrogen flow, and roasting for 6-12h to obtain a precursor B.
And S3, adding the precursor B into a strong alkaline solution for heating reaction, and washing and drying after the reaction is finished to obtain lignin carbon.
The strong alkaline solution is sodium hydroxide solution, and the temperature of the heating reaction is 80 ℃.
S4, dropwise adding the aqueous solution of the halogen salt into the aqueous solution of the bismuth salt and the lignin carbon at the speed of 1-10 drops/second, uniformly mixing, regulating the pH (ammonia water) to 3-7, heating to 150-200 ℃ for reaction, centrifuging, washing, drying and grinding after the reaction is finished, and obtaining the lignin carbon-based bismuth oxyhalide composite material with regular flower-shaped morphology.
The halogen salt is a mixture of two of potassium chloride, potassium bromide and potassium iodide, and the dosage molar ratio of the halogen salt is 1:1-10:1.
Example 1 ]
5g of silica microspheres and 5g of alkali lignin are added into 50ml of ethylene glycol, and after ultrasonic mixing for 30min, the mixture is continuously stirred, heated and evaporated to dryness. Under the protection of nitrogen flow, heating to 800 ℃ at 5 ℃/min, and roasting for 12 hours to obtain the lignin carbon precursor. Adding the precursor into 50ml of concentrated sodium hydroxide solution, stirring for 6 hours at 80 ℃, centrifugally washing to be neutral, drying and grinding to obtain lignin carbon, and sealing and preserving.
6mmol of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) and 0.047g of lignin carbon are added into 30mL of deionized water and stirred for 30min to prepare solution A; 6mmol of potassium chloride (KCl) was added to 30mL of deionized water and stirred for 30min to prepare solution B. After the stirring, pouring the solution B into a separating funnel, dropwise adding the solution B into the solution A at a speed of 5 drops/second, stirring uniformly to form a mixed solution, regulating the PH to 3 by using ammonia water, and continuously stirring for 30min. The mixed solution was then transferred to a hydrothermal kettle and reacted at 200℃for 12h. Naturally cooling, centrifuging at 10000r/min, drying at 80deg.C for 12 hr, cooling to room temperature, grinding to obtain lignin carbon-based bismuth oxyhalide material 3% BiOCl@C, and sealing and preserving.
The SEM image in fig. 1 shows the composite material prepared in example 1. As can be seen from the figure, a large number of regular flower-like structures can be observed for all the products, with diameters ranging from 3 to 5. Mu.m. The SEM image of high magnification reveals the fine structure of the flower-like surface of the catalyst, which is composed of nanoplatelets, which are tightly bonded together to form a flower-like structure.
Example 2 ]
5g of silica microspheres and 5g of alkali lignin are added into 50ml of ethylene glycol, and after ultrasonic mixing for 30min, the mixture is continuously stirred, heated and evaporated to dryness. Under the protection of nitrogen flow, heating to 800 ℃ at 5 ℃/min, and roasting for 12 hours to obtain the lignin carbon precursor. Adding the precursor into 50ml of concentrated sodium hydroxide solution, stirring for 6 hours at 80 ℃, centrifugally washing to be neutral, drying and grinding to obtain lignin carbon, and sealing and preserving.
6mmol of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) and 0.047g of lignin carbon were added to 30mL of deionized water and stirred for 30min to prepare solution A. 3mmol of potassium bromide (KBr) and 3mmol of potassium chloride (KCl) were added to 30mL of deionized water and stirred for 30min to prepare solution B. After the stirring, pouring the solution B into a separating funnel, dropwise adding the solution B into the solution A at the speed of 2 drops/second, stirring uniformly to form a mixed solution, regulating the PH to 3 by using ammonia water, and continuously stirring for 30min. The mixed solution was then transferred to a hydrothermal kettle and reacted at 200℃for 12h. Naturally cooling, centrifuging at 10000r/min, drying at 80deg.C for 12 hr, cooling to room temperature, and grinding to obtain 3% BiOCl of lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology 0.5 Br 0.5 And C, sealing and storing.
Example 3 ]
5g of silica microspheres and 25g of alkali lignin are added into 50ml of ethylene glycol, and after ultrasonic mixing for 30min, the mixture is continuously stirred, heated and evaporated to dryness. Under the protection of nitrogen flow, heating to 1000 ℃ at 2 ℃/min, and roasting for 6 hours to obtain the lignin carbon precursor. Adding the precursor into 50ml of concentrated sodium hydroxide solution, stirring for 6 hours at 80 ℃, centrifugally washing to be neutral, drying and grinding to obtain lignin carbon, and sealing and preserving.
6mmol of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) and 0.047g of lignin carbon were added to 30mL of deionized water and stirred for 30min to prepare solution A. 3mmol of potassium bromide (KBr) and 3mmol of potassium iodide (KI) were added to 30mL of deionized water and stirred for 30min to prepare solution B. After the stirring, the solution B is poured into a separating funnel, and is added into the solution A dropwise at the speed of 10 drops/second, and the solution A is stirred until the solution A is uniform to form a mixed solution, the PH value of the mixed solution is regulated to 3 by ammonia water, and the mixed solution is continuously stirred for 30min. The mixed solution was then transferred to a hydrothermal kettle and reacted at 150℃for 12h. Naturally cooling, centrifuging at 10000r/min, drying at 80deg.C for 12 hr, cooling to room temperature, and grinding to obtain lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material 3 with regular flower-like morphology％BiOBr 0.5 I 0.5 And C, sealing and storing.
Example 4 ]
5g of silica microspheres and 50g of alkali lignin are added into 50ml of ethylene glycol, and after ultrasonic mixing for 30min, the mixture is continuously stirred, heated and evaporated to dryness. Under the protection of nitrogen flow, heating to 500 ℃ at 1 ℃/min, and roasting for 8 hours to obtain the lignin carbon precursor. Adding the precursor into 50ml of concentrated sodium hydroxide solution, stirring for 6 hours at 80 ℃, centrifugally washing to be neutral, drying and grinding to obtain lignin carbon, and sealing and preserving.
6mmol of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) and 0.047g of lignin carbon were added to 30mL of deionized water and stirred for 30min to prepare solution A. 3mmol of potassium chloride (KCl) and 3mmol of potassium iodide (KI) were added to 30mL of deionized water, and stirred for 30min to prepare a solution B. After the stirring, the solution B is poured into a separating funnel, and is added into the solution A dropwise at the speed of 10 drops/second, and the solution A is stirred until the solution A is uniform to form a mixed solution, the PH value of the mixed solution is regulated to 3 by ammonia water, and the mixed solution is continuously stirred for 30min. The mixed solution was then transferred to a hydrothermal kettle and reacted at 180℃for 10 hours. Naturally cooling, centrifuging at 10000r/min, drying at 80deg.C for 12 hr, cooling to room temperature, and grinding to obtain 3% BiOCl of lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology 0.5 I 0.5 And C, sealing and storing.
Comparative example 1 ]
5g of silica microspheres and 5g of alkali lignin are added into 50ml of ethylene glycol, and after ultrasonic mixing for 30min, the mixture is continuously stirred, heated and evaporated to dryness. Heating to 800 ℃ at 30 ℃/min under the protection of nitrogen flow, and roasting for 12 hours to obtain the lignin carbon precursor. Adding the precursor into 50ml of concentrated sodium hydroxide solution, stirring for 6 hours at 80 ℃, centrifugally washing to be neutral, drying and grinding to obtain lignin carbon, and sealing and preserving.
6mmol of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) and 0.047g of lignin carbon were added to 30mL of deionized water and stirred for 30min to prepare solution A. 3mmol of potassium bromide (KBr) and 3mmol of potassium chloride (KCl) were added to 30mL of deionized water and stirred for 30min to prepare solution B. Stirring is finishedThen pouring the solution B into a separating funnel, gradually adding the solution B into the solution A at the speed of 2 drops/second, stirring to be uniform to form a mixed solution, regulating the PH to be 3 by using ammonia water, and continuously stirring for 30min. The mixed solution was then transferred to a hydrothermal kettle and reacted at 200℃for 12h. Naturally cooling, centrifuging at 10000r/min, drying at 80deg.C for 12 hr, cooling to room temperature, and grinding to obtain 3% BiOCl of lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology 0.5 Br 0.5 And C, sealing and storing.
Comparative example 2 ]
5g of silica microspheres and 5g of alkali lignin are added into 50ml of ethylene glycol, and after ultrasonic mixing for 30min, the mixture is continuously stirred, heated and evaporated to dryness. Under the protection of nitrogen flow, heating to 800 ℃ at 5 ℃/min, and roasting for 12 hours to obtain the lignin carbon precursor. Adding the precursor into 50ml of concentrated sodium hydroxide solution, stirring for 6 hours at 80 ℃, centrifugally washing to be neutral, drying and grinding to obtain lignin carbon, and sealing and preserving.
6mmol of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) and 0.047g of lignin carbon were added to 30mL of deionized water and stirred for 30min to prepare solution A. 3mmol of potassium bromide (KBr) and 3mmol of potassium chloride (KCl) were added to 30mL of deionized water and stirred for 30min to prepare solution B. After the stirring, pouring the solution B into a separating funnel, dropwise adding the solution B into the solution A at a speed of 20 drops/second, stirring uniformly to form a mixed solution, regulating the PH to 3 by using ammonia water, and continuously stirring for 30min. The mixed solution was then transferred to a hydrothermal kettle and reacted at 200℃for 12h. Naturally cooling, centrifuging at 10000r/min, drying at 80deg.C for 12 hr, cooling to room temperature, and grinding to obtain 3% BiOCl of lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology 0.5 Br 0.5 And C, sealing and storing.
Comparative example 3 ]
5g of silica microspheres and 5g of alkali lignin are added into 50ml of ethylene glycol, and after ultrasonic mixing for 30min, the mixture is continuously stirred, heated and evaporated to dryness. Under the protection of nitrogen flow, heating to 800 ℃ at 5 ℃/min, and roasting for 12 hours to obtain the lignin carbon precursor. Adding the precursor into 50ml of concentrated sodium hydroxide solution, stirring for 6 hours at 80 ℃, centrifugally washing to be neutral, drying and grinding to obtain lignin carbon, and sealing and preserving.
6mmol of bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O) and 0.047g of lignin carbon were added to 30mL of deionized water and stirred for 30min to prepare solution A. 3mmol of potassium bromide (KBr) and 3mmol of potassium chloride (KCl) were added to 30mL of deionized water and stirred for 30min to prepare solution B. After the stirring was completed, the solution B was poured into a separating funnel, and was added dropwise to the solution A at a rate of 2 drops/sec, and after stirring to uniformity, a mixed solution was formed, and stirring was continued for 30 minutes with pH adjusted to 10. The mixed solution was then transferred to a hydrothermal kettle and reacted at 200℃for 12h. Naturally cooling, centrifuging at 10000r/min, drying at 80deg.C for 12 hr, cooling to room temperature, and grinding to obtain 3% BiOCl of lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology 0.5 Br 0.5 And C, sealing and storing.
< detection of photocatalytic Properties >
20mg of BiOCl, the composite materials prepared in examples 1 and 2 and comparative examples 1 to 3 were weighed respectively, placed in a special quartz reactor, and 50ml of methylene blue MB solution and rhodamine RhB (20 mg/L) were added respectively under a dark condition. The reactor was transferred to 500W xenon lamp illumination at room temperature for 3h, sampled every 20 min. The samples were tested using a Pu-XU 6 New century UV-visible spectrophotometer and the absorbance of each sample was measured at 664nm absorption wavelength.
FIGS. 2 (a, b) show XRD spectra before and after photocatalytic degradation of MB and RhB for 3h with BiOCl and 3% BiOCl@C, respectively, as shown in the figure, the structures of BiOCl and 3% BiOCl@C crystal forms are unchanged before and after the reaction, which illustrates the stability of the PbFCl type structure of the bismuth oxyhalide material.
In FIG. 3, bismuth oxyhalide materials 3% BiOCl@C (example 1) and 3% BiOCl 0.5 Br 0.5 Ultraviolet-visible diffuse reflectance spectra of samples @ C (example 2), 3% BiOCl @ C and 3% BiOCl 0.5 Br 0.5 The @ C sample showed a strong light absorption throughout the visible region. The sample lignin carbon material in the figure does not show strong light absorption in the whole visible light region. By data analysisIt is known that the forbidden band width eg=3.14 eV of 3% biocl@c, 3% biocl 0.5 Br 0.5 The forbidden band width eg=2.92 eV of @ C, the forbidden band width of both materials is smaller than BiOCl, indicating that the formation of the flower-like structure and the Z-type heterojunction enhances the visible light response of the material.
FIG. 4 shows 3% BiOCl 0.5 Br 0.5 The catalyst @ C (example 2) significantly improved the degradation rate of the organic dye, which was 96.8% and 81.3% for MB and RhB, respectively; 3% BiOCl@C (example 1) showed 83.6% degradation of MB and 62.7% degradation of RhB.
When lignin carbon and bromine elements are not added into the system, the degradation rate of BiOCl on MB and RhB is respectively 37.3% and 46.2%, and the degradation effect is not obvious.
This illustrates that the combined action of the flower-like structure and the Z-type heterojunction results in improved performance of the catalyst, which can be attributed to the following two aspects. On one hand, the regular flower-shaped structure of the material realizes the space separation of the BiOX nano-sheets, increases the specific surface area of the material, greatly improves the contact area between the BiOX material and pollutants, and strengthens the photocatalytic reaction. Second, biOX is formed when two halogen salts are hydrothermally mixed n Y 1-n The Z-shaped heterojunction is generated between the two semiconductors with similar structures, the separation of photo-generated electrons and holes is promoted, the visible light response of the material is expanded, and the two effects act cooperatively to ensure that the catalyst achieves the optimal photocatalytic performance.
The degradation rates of the catalyst of comparative example 1 on MB and RhB were 72.6% and 66.4%, respectively. The degradation rates of the catalyst of comparative example 2 on MB and RhB were 78.2% and 68.3%, respectively. The degradation rates of the catalyst of comparative example 3 on MB and RhB were 46.6% and 62.5%, respectively.
The degradation rates of the catalysts in comparative examples 1-3 on MB and RhB are reduced compared with those in example 2, which shows that the specific rich oxygen-containing functional groups of lignin can be effectively reserved by adopting medium-temperature roasting with controlled heating rate, and then the oxygen-containing functional groups on the surface of lignin are formed into hydroxyl groups for electron supply and attracted halogen ions for electron attraction to attract each other by combining with controlled dropping speed and PH regulation, so that the space separation of BiOX nanosheets is realized, flower-like morphology is formed, and the energy barrier of photo-generated electron-hole recombination is improved.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (10)
1. The preparation method of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with the regular flower-shaped morphology is characterized by comprising the following steps of:
s1, dissolving a template agent and lignin in ethylene glycol together, carrying out ultrasonic dispersion and mixing, and then heating and evaporating to dryness to obtain a raw material A;
s2, heating the raw material A to 500-1000 ℃ at a heating rate of 1-5 ℃/min under the protection of nitrogen flow, and roasting for 6-12h to obtain a precursor B;
s3, adding the precursor B into a strong alkaline solution for heating reaction, and washing and drying after the reaction is finished to obtain lignin carbon;
s4, dropwise adding the aqueous solution of the halogen salt into the aqueous solution of the bismuth salt and the lignin carbon at the speed of 1-10 drops/second, uniformly mixing, regulating the pH value to 3-7, heating to 150-200 ℃ for reaction, centrifuging, washing, drying and grinding after the reaction is finished, and obtaining the lignin carbon-based bismuth oxyhalide composite material with regular flower-shaped morphology.
2. The method for preparing the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology as claimed in claim 1, which is characterized in that: the template agent in the step S1 is silica microspheres, and lignin is alkali lignin.
3. The method for preparing the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology as claimed in claim 2, which is characterized in that: the mass ratio of the silica microspheres to the alkali lignin is 1:1-1:10.
4. The method for preparing the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology as claimed in claim 1, which is characterized in that: the halogen salt in the step S4 is potassium chloride, potassium bromide or potassium iodide.
5. The method for preparing the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology as claimed in claim 1, which is characterized in that: the halogen salt in the step S4 is a mixture of any two of potassium chloride, potassium bromide and potassium iodide.
6. The method for preparing the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology as claimed in claim 5, which is characterized in that: the molar ratio of the two halogen salts is 1:1-10:1.
7. The method for preparing the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology as claimed in claim 1, which is characterized in that: in the step S3, the strong alkaline solution is sodium hydroxide solution, and the heating reaction temperature is 80 ℃.
8. The method for preparing the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology as claimed in claim 1, which is characterized in that: in the step S4, ammonia water is used for adjusting the pH value of the solution.
9. A lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with a regular flower-like morphology, prepared by the method of any one of claims 1-8.
10. The use of the lignin carbon-based bismuth oxyhalide Z-type heterojunction composite material with regular flower-like morphology according to claim 9 in a system for photocatalytic degradation of organic pollutants.
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| CN115779889A (en) * | 2022-11-10 | 2023-03-14 | 中国林业科学研究院林产化学工业研究所 | Lignin carbon/bismuth molybdate composite photocatalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115779889A (en) * | 2022-11-10 | 2023-03-14 | 中国林业科学研究院林产化学工业研究所 | Lignin carbon/bismuth molybdate composite photocatalyst and preparation method and application thereof |
| CN115779889B (en) * | 2022-11-10 | 2024-05-03 | 中国林业科学研究院林产化学工业研究所 | Lignin charcoal/bismuth molybdate composite photocatalyst and preparation method and application thereof |
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