CN109092306B - Preparation method of LSPR effect-based metal-modified self-doped defect-rich tin oxide nanocomposite - Google Patents
Preparation method of LSPR effect-based metal-modified self-doped defect-rich tin oxide nanocomposite Download PDFInfo
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- 230000007547 defect Effects 0.000 title claims abstract description 55
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 47
- 230000000694 effects Effects 0.000 title claims abstract description 43
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 238000003760 magnetic stirring Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 24
- 239000011780 sodium chloride Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 8
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- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical compound [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
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- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 6
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 5
- 229910052697 platinum Inorganic materials 0.000 abstract description 5
- 229910052709 silver Inorganic materials 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 229910052737 gold Inorganic materials 0.000 abstract description 3
- 239000002923 metal particle Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
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- 239000000243 solution Substances 0.000 description 66
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
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- 230000031700 light absorption Effects 0.000 description 5
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- 229910006702 SnO2-x Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910003081 TiO2−x Inorganic materials 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
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- 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 2
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- LCALOJSQZMSPHJ-QMMMGPOBSA-N (2s)-2-amino-3-cyclohexa-1,5-dien-1-ylpropanoic acid Chemical compound OC(=O)[C@@H](N)CC1=CCCC=C1 LCALOJSQZMSPHJ-QMMMGPOBSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 229910015675 MoO3−x Inorganic materials 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SPCNPOWOBZQWJK-UHFFFAOYSA-N dimethoxy-(2-propan-2-ylsulfanylethylsulfanyl)-sulfanylidene-$l^{5}-phosphane Chemical compound COP(=S)(OC)SCCSC(C)C SPCNPOWOBZQWJK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
A preparation method of a metal-modified self-doped defect-rich tin oxide nanocomposite based on LSPR effect comprises the steps of modifying nano metal particles with plasma resonance effect on a nano composite photocatalyst material on the self-doped defect-rich tin oxide through chemical bond complexation; the self-doped defect-rich tin oxide is selected from Sn-doped non-stoichiometric or mixed valence oxygen-rich defect tin oxide (SnO)2‑x) (ii) a The nano metal with the plasma resonance effect is selected from metal nano particles of single-component metal or multi-component alloy with the plasma resonance effect, such as Pt, Au, Ag, Cu and the like. The invention fully improves the separation rate of photo-generated electrons and holes in the photocatalytic reaction by utilizing the visible light photocatalytic oxidation reduction characteristic of the self-doped defect-rich tin oxide, the plasma resonance effect of the metal nano particles and the heterojunction structure with chemical bonding between the two components, thereby being beneficial to improving the performance of degrading pollutants by photocatalytic oxidation reduction and decomposing water to produce hydrogen by photocatalysis.
Description
Technical Field
The invention relates to a preparation method of a tin oxide nano composite material, in particular to a preparation method of a metal modified self-doped defect-rich tin oxide nano composite material based on an LSPR effect.
Background
Currently, the research progress of the photocatalytic technology brings hope and power to people, but the improvement of the efficiency of the photocatalytic technology is still a challenge. The development of catalytic materials with solar energy broad spectrum absorption, high carrier separation rate and strong oxidation reduction capability is the key to realize the high-efficiency water photolysis technology[Method for producing hydrogen by utilizing solar energy and development status [ J ] of Chen-Hongshan-Weihua]Material guide 2015,29(11):36-40.][Ran,J.,Zhang,J.,Yu,J.,Jaroniec,M.,Qiao,S.Z.Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting[J].Chemical Society Reviews,2014,43(22):7787-7812.]However, it is difficult for a single or unmodified semiconductor material to satisfy the above three requirements simultaneously. The reason is that: first, the light absorption capacity and the redox capacity of a single semiconductor material often cannot be improved simultaneously; meanwhile, some single-component semiconductor materials (such as CdS and MoS) with excellent visible light response and strong oxidation reduction capability2Etc.) have drawbacks in light stability and environmental friendliness; in addition, the rate of the photolytic water reaction is inhibited by high carrier recombination in the single component catalyst material.
The oxygen hole in the self-doped defect-rich tin oxide is taken as an electron capture center, which is favorable for promoting the separation of photo-generated electrons and holes, thereby promoting the photocatalytic reaction of the tin oxide [ Shileyu, Liumeiling, Lixintong, and the like]2016 (45 to 6):7-8.]. Structural characteristics of oxygen-rich vacancy defects enable SnO2-xThe nano-particles show excellent performance of hydrogen production by water photolysis (133.8 mu mol.h) compared with P25 and ZnO-1·g-1)[Li,M.,Hu,Y.,Xie,S.,Huang,Y.,Tong,Y.,Lu,X.Heterostructured ZnO/SnO2-x nanoparticles for efficient photocatalytic hydrogen production[J].Chemical Communications,2014,50(33):4341-4343.]. Sn self-doping SnO2-xThe existence of oxygen defects in the nanocrystal can effectively improve the separation of photo-generated electron-hole pairs, thereby obtaining excellent dye photocatalytic degradation performance [ Han, D, Jiang, B, Feng, J, Yin, Y, Wang, W2-x Nanocrystals Drive Visible-Light-Responsive Color Switching[J].Angewandte Chemie International Edition,2017,56(27):7792-7796.]. At the same time, the band gap width of the non-stoichiometric or mixed-valence tin oxide is larger than that of the monovalent SnO2Has a smaller band gap width and thus exhibits more excellent photocatalytic properties, such as Sn2O3、Sn3O4And Sn5O6. In literature reports, stannous oxide (SnO) has strong reducibility, is used for preparing catalysts, reducing agents and the like, and is used for preparing stannous fluoborate and other soluble stannous salts in electroplating. Multiple stagesNanostructured Sn3O4Realizes the 30 percent degradation of methyl orange within 30min under the condition of sunlight irradiation [ Song, H, Son, S.Y., Kim, S.K.,&Jung,G.Y.A facile synthesis of hierarchical Sn3O4nanostructures in an acidic aqueous solution and their strong visible-light-driven photocatalytic activity.Nano Research,2015,8(11),3553-3561.]。
in order to obtain composite materials with closer energy level structures, tin oxide composite photocatalytic materials with different stoichiometric ratios are designed and prepared. SnO/Sn3O4The heterostructure has a specific composition of single-component SnO and single-component Sn3O4More excellent rhodamine B photocatalytic degradation performance [ the Torricelli, the Poplar silk, the Hodson, the Shipu SnO/Sn3O4Preparation of heterostructure and its photocatalytic performance functional material, 2017,48(1), 1159-.]. And SnO/Sn3O4Heterostructures have superior photocatalytic degradation of rhodamine B performance [ Xia, w., Wang, h., Zeng, x., Han, j., Zhu, j., Zhou, m.,&Wu,S.High-efficiency photocatalytic activity of type II SnO/Sn3O4heterostructures via interfacial charge transfer.CrystEngComm,2014,16(30),6841-6847.]。
however, the photogenerated electron-hole separation rate of the materials is still not optimized, and the materials have the defect of low stability, so that the further improvement of the photocatalytic performance is inhibited.
Localized Surface Plasmon Resonance (LSPR) [ (Boerigter, C., Campana, R., Morabito, M., Linear, S.Evaporation and simulations of direct charge excitation as the dominant charge in plasma-mediated catalysis [ J. ]].Nature communications,2016,7:10545.]Preparation of novel plasma photocatalyst nano gold-zinc titanate compound and hydrogen production performance by photolysis of water [ J]Application chemistry, 2016,33(5):583-590.]Is the free carrier bulk oscillation effect caused by the illumination excitation of the nano particles, which leads the nano material to have the unique characteristics of selective light absorption and near field enhancementPhysical properties. plasma-Induced carrier Separation (PICS) based on LSPR (localized surface Plasmon resonance) [ Clavero, C].Nature Photonics,2014,8(2):95.]The photon-generated carrier recombination in the semiconductor material can be effectively inhibited. In addition, the LSPR effect can also improve the photothermal Conversion efficiency of semiconductors, accelerate the activation of reactant molecules, and further improve the photocatalytic reaction rate [ Meng, X, Liu, L, Ouyang, S, Xu, H, Wang, D, ZHao, N, Ye, J.nanometals for solvent-to-Chemical Energy Conversion: From Semiconductor-Based photocatalytic to plasma-media photocatalytic and Photo-thermal catalysis [ J.Nanometallals].Advanced Materials,2016,28(32):6781-6803.]. The Zhaokeri subject group invents a preparation method of a nanocluster utilizing a plasma resonance effect and an electron transport synergistic effect, and obtains a composite photocatalytic material with a good photoelectric effect [ Zhang TieRui, Cao tiger, Wu Li bead, and the like, a nanocluster photocatalyst utilizing a surface plasma resonance effect and an electron transport synergistic effect, and a preparation method and application thereof are shown in CN104437561A [ P].2015.]. At present, the materials with stronger LSPR effect mainly comprise metal nanoparticles such as Pt, Au, Ag and Cu and the like, and partial non-metal compounds (such as CuS and WO)3-xAnd MoO3-xEtc.) while also exhibiting LSPR effects and being relatively low cost, the low carrier concentration makes it difficult to achieve an effective PICS. The preparation of the self-doping defect-rich tin oxide composite material modified by the metal with the plasma resonance effect by selecting the metal nanoparticles (such as Pt, Au, Ag, Cu and the like) has many advantages in the aspects of environmental friendliness, strong catalytic activity, high stability and the like.
In order to maximize plasmon-induced carrier separation by the plasmon resonance effect of the metal nanoparticles through the photoelectric effect, it is important to select a semiconductor material that coincides with the plasmon resonance light absorption range of the metal nanoparticles and is excellent in photoelectric transmission and photochemical stability. The self-doped defect-rich tin oxide has the advantages, so that the self-doped defect-rich tin oxide is one of ideal semiconductor materials which have the most potential at present and realize high-efficiency solar broad-spectrum photocatalysis through plasma resonance photosensitization. Considering that the oxygen vacancy defect enables the self-doped tin oxide to have excellent photoelectric transmission capacity and an energy level structure which is beneficial to photolysis of water to produce hydrogen, the plasma resonance effect expands the remarkable effect of the visible light and near infrared light response capacity of the catalyst, and the coupling effect of the metal nanoparticle plasma resonance and the self-doped tin oxide oxygen vacancy defect is beneficial to enhancing the solar photocatalytic performance of the metal modified self-doped defect-rich tin oxide.
In recent years, the synergistic effect of plasmon resonance and oxygen vacancy defects has significantly promoted the photocatalytic reaction of some semiconductor materials. The Au/BiOCl plasma resonance photocatalyst [ Li, H., Qin, F., Yang, Z., Cui, X., Wang, J., Zhang, L.New reaction path induced by plasma for selective benzyl alcohol oxidation on BiOCl stress oxidation catalysts [ J.J. reaction pathways ] was prepared by the professor of Wang building of Chinese university in hong Kong and the professor of Zhang university in Huazhong university in China].Journal of the American Chemical Society,2017,139(9):3513-3521.]The BiOCl oxygen vacancy promotes the separation of hot carriers on the surface of the nano Au by capturing hot electrons, and a local electric field induced by a plasma resonance effect enhances the rapid transfer of interface photo-generated electrons, so that the photocatalytic oxidation of the efficient benzyl alcohol is realized. BiVO of professor Dong dawn Lily of Dalian industry university for oxygen-rich vacancy4The silver nano-particles are deposited with bismuth vanadate containing oxygen vacancies to improve the near infrared light catalytic performance [ J]The catalytic journal, 2017,39(1):128-137.]The plasma resonance effect of Ag enhances the visible light response of the material, BiVO4The oxygen vacancies effectively trap electrons and facilitate the separation of photogenerated carriers. The King-Ownship researcher of Chinese academy of sciences made Ag/TiO through photoreduction and subsequent heat treatment2-x[Duan,Y.,Zhang,M.,Wang,L.,Wang,F.,Yang,L.,Li,X.,Wang,C.Plasmonic Ag-TiO2-x nanocomposites for the photocatalytic removal of NO under visible light with high selectivity:The role of oxygen vacancies[J].Applied Catalysis B:Environmental,2017,204:67-77.]The plasma resonance effect enables the material to have excellent visible light response and high-efficiency photon-generated carrier separation rate, and meanwhile, TiO2-xWith NO promoted by oxygen vacancy defectsAnd the synergistic enhancement of the oxygen vacancy defect and the NO photocatalytic removal by the plasma resonance is realized by the photoreduction. The research shows that the coupling effect of metal plasma resonance and oxygen vacancy defect of semiconductor material is favorable for enhancing the photocatalytic performance of the composite material.
Disclosure of Invention
The invention aims to provide a preparation method of a metal-modified self-doping defect-rich tin oxide nano composite material based on an LSPR effect, namely, the metal-modified self-doping defect-rich tin oxide nano composite photocatalytic material based on the LSPR effect, which has controllable appearance, high dispersion degree, uniform granularity and tight interface combination, is prepared by adopting a wet chemical in-situ synthesis method.
In order to achieve the purpose, the invention adopts the technical scheme that:
1) 1mmol of analytically pure stannous methanesulfonate ((CH)3SO3)2Sn) and 3.2-8.7 mmol of citric acid are fully dissolved in 4-10 mL of absolute ethyl alcohol, then 0.5-9 mmol of phytic acid and 10-25 mL of deionized water are sequentially added, and then the pH value is adjusted to 4-10 by using NaOH solution to obtain solution A;
2) 0-1 mmol of analytically pure chloroplatinic acid (H) is taken2PtCl6) 0 to 2mmol of chloroauric acid (HAuCl)4) 0-5 mmol of silver nitrate (AgNO)3) 0 to 10mmol of copper nitrate (Cu (NO)3)2) And 1-15 mmol of citric acid are fully dissolved in 8-20 mL of deionized water and uniformly mixed to obtain a solution B;
3) dropwise adding the solution B into the solution A at a speed of 30-60 drops/min to obtain a hydrothermal reaction precursor solution;
4) transferring the precursor solution into a hydrothermal kettle with a polytetrafluoroethylene lining, uniformly introducing nitrogen into the precursor solution, immediately sealing the hydrothermal kettle after the nitrogen introduction is finished, and then placing the reaction kettle into a constant-temperature oven to keep the temperature of 80-180 ℃ for 2-48 h;
5) after the hydrothermal reaction is finished and the reaction system is naturally cooled to room temperature, centrifugally separating the product, washing the product by using deionized water and absolute ethyl alcohol in sequence, and finally washing the product at 35-65 ℃ and under the vacuum degree of 10-1～10-3Drying in a vacuum drying oven of Pa to obtainThe self-doping defect-rich tin oxide nano composite material is modified by metal based on LSPR effect.
The concentration of the NaOH solution in the step 1) is 0.5-10 mol/L.
And in the whole process of the step 1), a constant-temperature magnetic stirring device is used for continuously magnetically stirring NaCl and crushed ice in an ice salt bath at the temperature of-20-10 ℃.
The step 2) is to add chloroplatinic acid (H)2PtCl6) Chloroauric acid (HAuCl)4) Silver nitrate (AgNO)3) Copper nitrate (Cu (NO)3)2) And citric acid are fully dissolved in deionized water, and then the solution is subjected to continuous magnetic stirring and uniform mixing in an ice salt bath of NaCl and crushed ice at the temperature of-20-10 ℃ by using a constant-temperature magnetic stirring device to obtain a solution B.
And 3) carrying out continuous magnetic stirring for 10-12 h in an ice salt bath of NaCl and crushed ice at the temperature of-20-10 ℃ in the whole dripping process.
The filling ratio in the step 4) is 40-70%.
And 4) uniformly introducing nitrogen into the forward driving liquid by using 0.1-0.5 Mpa of airflow, wherein the nitrogen introducing time is 10-60 min.
And 5) washing 3-8 times by using deionized water and absolute ethyl alcohol respectively.
And 5) drying for 2-10 h.
The invention adopts two effects of metal plasma resonance photosensitization and oxygen vacancy defect adjustment semiconductor energy level structure to synergistically promote the photocatalytic reaction of the metal-modified self-doped defect-rich tin oxide nanocomposite material to obtain high-efficiency and stable photocatalytic performance. On one hand, the adjustment of the oxygen vacancy defect concentration can realize the adjustment of the self-doped defect-rich tin oxide energy level structure to improve the oxidation reduction capability of the self-doped defect-rich tin oxide energy level structure, and the construction of the defect energy level can also realize the capture and storage of photogenerated electrons so as to effectively improve the service life of a photogenerated carrier and enable the self-doped defect-rich tin oxide to have stronger visible light water decomposition performance. On the other hand, the loaded metal nanoparticles with the plasma resonance effect can expand the solar energy broad spectrum light absorption capacity to the visible light and near infrared light range while maintaining the oxidation reduction capacity of the self-doped defect-rich tin oxide. Meanwhile, the oxygen-rich vacancy defect structure has a positive effect on improving the conductivity of the self-doped defect-rich tin oxide, and the introduction of metal nanoparticles serving as electron acceptors into the self-doped defect-rich tin oxide is also an effective strategy for improving the charge separation of the composite material.
Compared with the existing preparation method, the metal-modified self-doping defect-rich tin oxide nano composite photocatalytic material prepared by adopting a wet chemical in-situ synthesis method has the advantages of high stability, good dispersibility, narrow particle size distribution, complete crystal development, controllable appearance and size, simple and efficient process, tight interface combination and the like, effectively solves the problem that metal particles in the traditional metal-loaded semiconductor composite photocatalytic material are easy to move and fall off, and obtains more efficient photocatalytic performance.
The invention has the beneficial effects that:
1) the preparation method of the metal-modified self-doping defect-rich tin oxide nano composite photocatalytic material based on the plasma resonance effect has the advantages of simple process control, low cost and low preparation temperature, does not need post-heat treatment, and avoids the defects of grain growth, coarsening, curling and the like possibly caused in the post-heat treatment process to a certain extent.
2) The metal-modified self-doped defect-rich tin oxide nano composite photocatalytic material based on the plasma resonance effect can realize tight interface combination, efficient separation of photo-generated electron-hole pairs on the interface structure and broad-spectrum light absorption in an ultraviolet-visible light region by utilizing good physicochemical compatibility and matched energy level structures among different components, thereby obtaining excellent performances of photocatalytic water decomposition hydrogen production and photocatalytic organic matter degradation.
3) The invention adopts a wet chemical in-situ synthesis method to realize the metal modified self-doped defect-rich tin oxide nanostructure composite photocatalytic material based on the plasma resonance effect, which has controllable appearance, high dispersibility, tight interface combination and uniform granularity.
Description of the drawings:
FIG. 1 is a projection electron microscope (TEM) image of a Pt/Ag alloy modified autodoped defect-rich tin oxide nanocomposite prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
1) 1mmol of analytically pure stannous methanesulfonate ((CH)3SO3)2Sn) and 3.2mmol of citric acid are fully dissolved in 4mL of absolute ethyl alcohol, then 0.5mmol of phytic acid and 10mL of deionized water are sequentially added, then 8mol/L of NaOH solution is used for regulating the pH value to be 10, and in the whole process, a constant-temperature magnetic stirring device is used for continuously and magnetically stirring the solution in an ice salt bath of NaCl and crushed ice at the temperature of minus 20 ℃ to obtain solution A;
2) 0.5mmol of analytically pure chloroplatinic acid (H) is taken2PtCl6) 1mmol of chloroauric acid (HAuCl)4) And 5mmol of citric acid are fully dissolved in 8mL of deionized water, and then are subjected to continuous magnetic stirring and uniform mixing in an ice salt bath of NaCl and crushed ice by using a constant-temperature magnetic stirring device at the temperature of-20 ℃ to obtain a solution B;
3) dropwise adding the solution B into the solution A at the speed of 30 drops/min, and performing continuous magnetic stirring for 12 hours in an ice salt bath of NaCl and crushed ice at the temperature of-20 ℃ in the whole dropwise adding process to obtain a hydrothermal reaction precursor solution;
4) transferring the precursor solution into a hydrothermal kettle with a polytetrafluoroethylene lining according to the filling ratio of 40%, uniformly introducing nitrogen into the precursor solution for 60min by using air flow of 0.1Mpa, immediately sealing the hydrothermal kettle after the nitrogen introduction is finished, and then placing the reaction kettle into a constant-temperature oven to keep the temperature at 180 ℃ for 5 h;
5) after the hydrothermal reaction is finished and the reaction system is naturally cooled to room temperature, the product is centrifugally separated, and is washed by deionized water and absolute ethyl alcohol respectively for 8 times, and finally, the reaction system is washed at 65 ℃ and the vacuum degree is 10-3And (4) drying in a vacuum drying oven of Pa for 4 hours to obtain the LSPR effect-based metal modified self-doped defect-rich tin oxide nano composite material.
Example 2:
1) 1mmol of analytically pure methanesulfonic acid is takenStannous ((CH)3SO3)2Sn) and 4mmol of citric acid are fully dissolved in 6mL of absolute ethyl alcohol, then 5mmol of phytic acid and 20mL of deionized water are sequentially added, then 4mol/L of NaOH solution is used for adjusting the pH value to be 6, and in the whole process, a constant-temperature magnetic stirring device is used for continuously and magnetically stirring the solution in a NaCl and crushed ice salt bath at-10 ℃ to obtain a solution A;
2) 0.2mmol of analytically pure chloroplatinic acid (H) is taken2PtCl6) 1.5mmol of silver nitrate (AgNO)3) And 7mmol of citric acid are fully dissolved in 13mL of deionized water, and then are subjected to continuous magnetic stirring and uniform mixing in a NaCl and crushed ice salt bath by using a constant-temperature magnetic stirring device at the temperature of-10 ℃ to obtain a solution B;
3) dropwise adding the solution B into the solution A at the speed of 40 drops/min, and performing continuous magnetic stirring for 11 hours in an ice salt bath of NaCl and crushed ice at the temperature of-10 ℃ in the whole dropwise adding process to obtain a hydrothermal reaction precursor solution;
4) transferring the precursor solution into a hydrothermal kettle with a polytetrafluoroethylene lining according to a filling ratio of 60%, uniformly introducing nitrogen into the precursor solution for 30min by using air flow of 0.3Mpa, immediately sealing the hydrothermal kettle after the nitrogen introduction is finished, and then placing the reaction kettle into a constant-temperature oven to keep the temperature at 130 ℃ for 15 h;
5) after the hydrothermal reaction is finished and the reaction system is naturally cooled to room temperature, the product is centrifugally separated, and is washed for 5 times by using deionized water and absolute ethyl alcohol respectively, and finally, the reaction system is washed for 5 times at 45 ℃ and the vacuum degree of 10-2And (5) drying in a vacuum drying oven of Pa for 6h to obtain the LSPR effect-based metal modified self-doped defect-rich tin oxide nano composite material.
As can be seen from figure 1, the composite material is composed of three components, namely Pt, Ag and self-doped defect-rich tin oxide, the three components are tightly combined, Pt and Ag in the composite material are nanoparticles, the diameter of the Pt nanoparticle is about 5-7 nm, the diameter of the Ag nanoparticle is about 8-10 nm, and the self-doped defect-rich tin oxide is of a nanosheet structure.
Example 3:
1) 1mmol of analytically pure stannous methanesulfonate ((CH)3SO3)2Sn) and 8.7mmol of citric acid are fully dissolved in 10mL of absolute ethyl alcohol, then 9mmol of phytic acid and 25mL of deionized water are sequentially added, then 1mol/L of NaOH solution is used for regulating the pH value to be 4, and in the whole process, a constant-temperature magnetic stirring device is used for continuously and magnetically stirring the solution in an ice salt bath of NaCl and crushed ice at 10 ℃ to obtain a solution A;
2) 0.5mmol of analytically pure chloroplatinic acid (H) is taken2PtCl6) 2mmol of silver nitrate (AgNO)3) 7mmol of copper nitrate (Cu (NO)3)2) And 12mmol of citric acid are fully dissolved in 20mL of deionized water, and then are subjected to continuous magnetic stirring and uniform mixing in a NaCl and crushed ice salt bath by using a constant-temperature magnetic stirring device at the temperature of 10 ℃ to obtain a solution B;
3) dropwise adding the solution B into the solution A at a speed of 60 drops/min, and carrying out continuous magnetic stirring for 12 hours in a NaCl and crushed ice salt bath at a temperature of 10 ℃ in the whole dropwise adding process to obtain a hydrothermal reaction precursor solution;
4) transferring the precursor solution into a hydrothermal kettle with a polytetrafluoroethylene lining according to a filling ratio of 70%, uniformly introducing nitrogen into the precursor solution for 20min by using air flow of 0.5Mpa, immediately sealing the hydrothermal kettle after the nitrogen introduction is finished, and then placing the reaction kettle into a constant-temperature oven to keep the temperature at 180 ℃ for 2 h;
5) after the hydrothermal reaction is finished and the reaction system is naturally cooled to room temperature, the product is centrifugally separated, and is washed by deionized water and absolute ethyl alcohol respectively for 8 times, and finally, the reaction system is washed at 65 ℃ and the vacuum degree is 10-1And (5) drying in a vacuum drying oven of Pa for 3h to obtain the LSPR effect-based metal modified self-doped defect-rich tin oxide nano composite material.
Example 4:
1) 1mmol of analytically pure stannous methanesulfonate ((CH)3SO3)2Sn) and 5mmol of citric acid are fully dissolved in 7mL of absolute ethyl alcohol, then 3mmol of phytic acid and 15mL of deionized water are sequentially added, then 0.5mol/L NaOH solution is used for adjusting the pH value to be 5, and the solution is continuously and magnetically stirred uniformly at-15 ℃ in an NaCl and crushed ice salt bath by using a constant-temperature magnetic stirring device in the whole process to obtain the solutionLiquid A;
2) 0.5mmol of analytically pure chloroauric acid (HAuCl) was taken4) 3mmol of silver nitrate (AgNO)3) 3mmol of copper nitrate (Cu (NO)3)2) And 1mmol of citric acid are fully dissolved in 10mL of deionized water, and then are subjected to continuous magnetic stirring and uniform mixing in an ice salt bath of NaCl and crushed ice by using a constant-temperature magnetic stirring device at the temperature of-15 ℃ to obtain a solution B;
3) dropwise adding the solution B into the solution A at the speed of 35 drops/min, and performing continuous magnetic stirring for 10 hours in a NaCl and crushed ice salt bath at the temperature of-15 ℃ in the whole dropwise adding process to obtain a hydrothermal reaction precursor solution;
4) transferring the precursor solution into a hydrothermal kettle with a polytetrafluoroethylene lining according to a filling ratio of 45%, uniformly introducing nitrogen into the precursor solution for 50min by using air flow of 0.4Mpa, immediately sealing the hydrothermal kettle after the nitrogen introduction is finished, and then placing the reaction kettle into a constant-temperature oven to keep the temperature of 80 ℃ for 48 h;
5) after the hydrothermal reaction is finished and the reaction system is naturally cooled to room temperature, the product is centrifugally separated, and is washed by deionized water and absolute ethyl alcohol for 3 times respectively, and finally the reaction system is washed at 35 ℃ and the vacuum degree is 10-2And (5) drying in a vacuum drying oven of Pa for 8 hours to obtain the LSPR effect-based metal modified self-doped defect-rich tin oxide nano composite material.
Example 5:
1) 1mmol of analytically pure stannous methanesulfonate ((CH)3SO3)2Sn) and 6mmol of citric acid are fully dissolved in 8mL of absolute ethyl alcohol, then 1mmol of phytic acid and 23mL of deionized water are sequentially added, then 3mol/L of NaOH solution is used for adjusting the pH value to be 8, and in the whole process, a constant-temperature magnetic stirring device is used for continuously and magnetically stirring the solution in a NaCl and crushed ice salt bath at 0 ℃ to obtain a solution A;
2) 1mmol of analytically pure chloroplatinic acid (H) was taken2PtCl6) 1.5mmol of chloroauric acid (HAuCl)4) 0.5mmol of silver nitrate (AgNO)3) 5mmol of copper nitrate (Cu (NO)3)2) And 10mmol of citric acid were dissolved in 15mL of deionized water sufficiently, and then the solution was subjected to an ice salt bath of NaCl and crushed iceThe solution B is obtained by continuously and uniformly stirring and mixing the solution B by using a constant-temperature magnetic stirring device under the temperature condition of 0 ℃;
3) dropwise adding the solution B into the solution A at the speed of 50 drops/min, and carrying out continuous magnetic stirring for 12 hours in a NaCl and crushed ice salt bath at the temperature of 0 ℃ in the whole dropwise adding process to obtain a hydrothermal reaction precursor solution;
4) transferring the precursor solution into a hydrothermal kettle with a polytetrafluoroethylene lining according to a filling ratio of 65%, uniformly introducing nitrogen into the precursor solution for 10min by using air flow of 0.2Mpa, immediately sealing the hydrothermal kettle after the nitrogen introduction is finished, and then placing the reaction kettle into a constant-temperature oven to keep the temperature at 100 ℃ for 40 h;
5) after the hydrothermal reaction is finished and the reaction system is naturally cooled to room temperature, the product is centrifugally separated, and is washed by deionized water and absolute ethyl alcohol for 6 times respectively, and finally the reaction system is washed at 55 ℃ and the vacuum degree is 10-3And (5) drying in a vacuum drying oven of Pa for 10h to obtain the LSPR effect-based metal-modified self-doped defect-rich tin oxide nano composite material.
Example 6:
1) 1mmol of analytically pure stannous methanesulfonate ((CH)3SO3)2Sn) and 7mmol of citric acid are fully dissolved in 5mL of absolute ethyl alcohol, then 7mmol of phytic acid and 18mL of deionized water are sequentially added, then 10mol/L of NaOH solution is used for adjusting the pH value to 9, and in the whole process, a constant-temperature magnetic stirring device is used for continuously and magnetically stirring the solution in a NaCl and crushed ice salt bath at 5 ℃ to obtain solution A;
2) 0.8mmol of analytically pure chloroplatinic acid (H) is taken2PtCl6) 2mmol of chloroauric acid (HAuCl)4) 5mmol of silver nitrate (AgNO)3) 10mmol of copper nitrate (Cu (NO)3)2) And 15mmol of citric acid are fully dissolved in 18mL of deionized water, and then are subjected to continuous magnetic stirring and uniform mixing in an ice salt bath of NaCl and crushed ice at the temperature of 5 ℃ by using a constant-temperature magnetic stirring device to obtain a solution B;
3) dropwise adding the solution B into the solution A at a speed of 45 drops/min, and carrying out continuous magnetic stirring for 11h in a NaCl and crushed ice salt bath at the temperature of 5 ℃ in the whole dropwise adding process to obtain a hydrothermal reaction precursor solution;
4) transferring the precursor solution into a hydrothermal kettle with a polytetrafluoroethylene lining according to the filling ratio of 50%, uniformly introducing nitrogen into the precursor solution for 40min by using air flow of 0.5Mpa, immediately sealing the hydrothermal kettle after the nitrogen introduction is finished, and then placing the reaction kettle into a constant-temperature oven to keep the temperature at 150 ℃ for 24 h;
5) after the hydrothermal reaction is finished and the reaction system is naturally cooled to room temperature, the product is centrifugally separated, and is washed for 7 times by using deionized water and absolute ethyl alcohol respectively, and finally, the reaction system is washed for 10 times at 60 ℃ and the vacuum degree-1And (5) drying in a vacuum drying oven of Pa for 2h to obtain the LSPR effect-based metal modified self-doped defect-rich tin oxide nano composite material.
Claims (5)
1. A preparation method of a metal-modified self-doping defect-rich tin oxide nanocomposite based on an LSPR effect is characterized by comprising the following steps:
1) 1mmol of analytically pure stannous methanesulfonate ((CH)3SO3)2Sn) and 3.2-8.7 mmol of citric acid are fully dissolved in 4-10 mL of absolute ethyl alcohol, then 0.5-9 mmol of phytic acid and 10-25 mL of deionized water are sequentially added, then the pH value of the solution is adjusted to 4-10 by using a NaOH solution, and in the whole process, a constant-temperature magnetic stirring device is used for continuously and magnetically stirring the solution in an ice salt bath of NaCl and crushed ice at-20-10 ℃ to obtain a solution A;
2) 0-1 mmol of analytically pure chloroplatinic acid (H) is taken2PtCl6) 0 to 2mmol of chloroauric acid (HAuCl)4) 0-5 mmol of silver nitrate (AgNO)3) 0 to 10mmol of copper nitrate (Cu (NO)3)2) And 1-15 mmol of citric acid are fully dissolved in 8-20 mL of deionized water, and then are subjected to continuous magnetic stirring and uniform mixing in a NaCl and crushed ice salt bath by using a constant-temperature magnetic stirring device at the temperature of-20-10 ℃ to obtain a solution B, wherein at least two of chloroplatinic acid, chloroauric acid or silver nitrate are added;
3) dropwise adding the solution B into the solution A at a speed of 30-60 drops/min, and carrying out continuous magnetic stirring for 10-12 h in an ice salt bath of NaCl and crushed ice at a temperature of-20-10 ℃ in the whole dropwise adding process to obtain a hydrothermal reaction precursor solution;
4) transferring the precursor solution into a hydrothermal kettle with a polytetrafluoroethylene lining, uniformly introducing nitrogen into the precursor solution for 10-60 min by using 0.1-0.5 Mpa airflow, immediately sealing the hydrothermal kettle after the nitrogen introduction is finished, and then placing the reaction kettle into a constant-temperature oven to keep the temperature at 80-180 ℃ for 2-48 h;
5) after the hydrothermal reaction is finished and the reaction system is naturally cooled to room temperature, centrifugally separating the product, washing the product by using deionized water and absolute ethyl alcohol in sequence, and finally washing the product at 35-65 ℃ and the vacuum degree of 10-1~10-3And drying in a vacuum drying box of Pa to obtain the LSPR effect-based metal-modified self-doped defect-rich tin oxide nano composite material.
2. The preparation method of the LSPR effect based metal modified self-doping defect-rich tin oxide nanocomposite material according to claim 1, wherein the method comprises the following steps: the concentration of the NaOH solution in the step 1) is 0.5-10 mol/L.
3. The preparation method of the LSPR effect based metal modified self-doping defect-rich tin oxide nanocomposite material according to claim 1, wherein the method comprises the following steps: the filling ratio in the step 4) is 40-70%.
4. The preparation method of the LSPR effect based metal modified self-doping defect-rich tin oxide nanocomposite material according to claim 1, wherein the method comprises the following steps: and 5) washing 3-8 times by using deionized water and absolute ethyl alcohol respectively.
5. The preparation method of the LSPR effect based metal modified self-doping defect-rich tin oxide nanocomposite material according to claim 1, wherein the method comprises the following steps: and 5) drying for 2-10 h.
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