CN106378158A - Preparation method of bismuth sulfide/titanium dioxide/graphene compound with high-catalysis degradation activity under visible light - Google Patents
Preparation method of bismuth sulfide/titanium dioxide/graphene compound with high-catalysis degradation activity under visible light Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 title claims abstract description 97
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 75
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 44
- 230000015556 catabolic process Effects 0.000 title claims abstract description 41
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 41
- 230000000694 effects Effects 0.000 title claims abstract description 30
- -1 graphene compound Chemical class 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 title description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 73
- 239000000725 suspension Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 230000001699 photocatalysis Effects 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 83
- 239000011941 photocatalyst Substances 0.000 abstract description 16
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 15
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract description 13
- 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 abstract description 12
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 abstract description 11
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 238000001782 photodegradation Methods 0.000 description 22
- 238000005119 centrifugation Methods 0.000 description 21
- 238000004729 solvothermal method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 11
- 238000002835 absorbance Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004690 nonahydrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229940079101 sodium sulfide Drugs 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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Abstract
一种在可见光下具有高催化降解活性的硫化铋/二氧化钛/石墨烯复合物的制法，属于光催化剂制备的技术领域。本发明采用钛酸四丁酯和氧化石墨烯为原料，以五水硝酸铋和九水硫化钠为硫化铋原料，经溶剂热和煅烧处理，最终得到硫化铋/二氧化钛/石墨烯复合物。合成的硫化铋/二氧化钛/石墨烯复合物对有机污染物的吸附能力增强，对可见光有较强的吸收能力，可延长电子‑空穴对的寿命，对有机污染物催化降解能力增强，其降解率是TiO2纳米颗粒的2.93倍，是硫化铋/TiO2的1.42倍，具有较高的实际应用价值。The invention discloses a method for preparing a bismuth sulfide/titanium dioxide/graphene compound with high catalytic degradation activity under visible light, belonging to the technical field of photocatalyst preparation. The invention adopts tetrabutyl titanate and graphene oxide as raw materials, bismuth nitrate pentahydrate and sodium sulfide nonahydrate as bismuth sulfide raw materials, and undergoes solvothermal and calcining treatment to finally obtain bismuth sulfide/titanium dioxide/graphene composite. The synthesized bismuth sulfide/titanium dioxide/graphene composite has enhanced adsorption capacity for organic pollutants, has a strong absorption capacity for visible light, can prolong the life of electron-hole pairs, and enhances the catalytic degradation ability for organic pollutants. The efficiency is 2.93 times that of TiO 2 nanoparticles and 1.42 times that of bismuth sulfide/TiO 2 , which has high practical application value.
Description
技术领域technical field
本发明涉及一种在可见光下具有高催化降解活性的硫化铋/二氧化钛/石墨烯复合物的制法，属于光催化剂制备的技术领域。The invention relates to a method for preparing a bismuth sulfide/titanium dioxide/graphene compound with high catalytic degradation activity under visible light, and belongs to the technical field of photocatalyst preparation.
背景技术Background technique
在催化和能源相关领域，TiO2很快受到很多科学家的关注。TiO2独特的电子能带结构和优良的表面活性赋予其在产氢、光伏、催化剂、锂离子电池、燃料电池、气体传感器、解毒、超级电容器等领域有广泛应用然而，TiO2相对较小的电荷转移能力和宽带隙(～3.2eV)是限制其应用的两个主要因素。为了克服这些问题采取了很多措施，如与其他半导体、金属非金属掺杂、与碳材料复合(RSC Advances，2014，4，1120-1127)等，使其对光吸收拓展至可见光区域以及延长光生电子空穴对的寿命。In the field of catalysis and energy, TiO 2 has quickly attracted the attention of many scientists. The unique electronic band structure and excellent surface activity of TiO 2 give it a wide range of applications in hydrogen production, photovoltaics, catalysts, lithium-ion batteries, fuel cells, gas sensors, detoxification, supercapacitors, etc. However, TiO 2 is relatively small Charge transfer capability and wide bandgap (~3.2eV) are the two main factors limiting their applications. In order to overcome these problems, many measures have been taken, such as doping with other semiconductors, metal and non-metal, and compounding with carbon materials (RSC Advances, 2014, 4, 1120-1127), etc., to extend the light absorption to the visible light region and prolong the light generation. The lifetime of the electron-hole pair.
石墨烯(Graphene)是一种由碳原子以sp2杂化轨道组成六角型呈蜂巢晶格的平面薄膜，只有一个碳原子厚度的二维材料，有优异的电、热和机械性能，在无机复合物中作为一种支撑材料和电子转移媒介，应用于电催化、超级电容、氢储备和光伏设备等不同领域。最近，大量研究表明，有较大比表面的石墨烯能做TiO2纳米材料的支撑体。与原始的TiO2相比，TiO2和石墨烯的复合增加了对污染物的吸收、扩展了光吸收区域、提高了载流子分离和转移效率(Applied Catalysis，B:Environmental，2014，144，893-899)，这样大大提高了其光催化性能。Graphene is a planar film composed of carbon atoms with sp 2 hybrid orbitals to form a hexagonal honeycomb lattice. It is a two-dimensional material with a thickness of only one carbon atom. It has excellent electrical, thermal and mechanical properties. As a support material and electron transfer medium in the composite, it can be applied in different fields such as electrocatalysis, supercapacitor, hydrogen storage and photovoltaic devices. Recently, a large number of studies have shown that graphene with a large specific surface can be used as a support for TiO 2 nanomaterials. Compared with the original TiO 2 , the combination of TiO 2 and graphene increases the absorption of pollutants, expands the light absorption area, and improves the carrier separation and transfer efficiency (Applied Catalysis, B: Environmental, 2014, 144, 893-899), which greatly improved its photocatalytic performance.
此外，通过与半导体的结合形成异质结构，也可以增加对可见光的吸收，抑制光生电子-空穴对的复合，使TiO2/石墨烯复合物的光催化活性进一步得到增强。比如有研究(Journal of Physical Chemistry C，2013，40，20406-20414)报道了CdS复合TiO2纳米颗粒与石墨烯的复合可有效提高TiO2的光催化活性，应用于复杂的光电极、太阳能电池、制氢等领域。基于此背景，本发明合成了一种在可见光下具有高催化降解活性的硫化铋/二氧化钛/石墨烯复合物光催化剂。In addition, by combining with semiconductors to form a heterostructure, it can also increase the absorption of visible light, inhibit the recombination of photogenerated electron-hole pairs, and further enhance the photocatalytic activity of TiO 2 /graphene composites. For example, some studies (Journal of Physical Chemistry C, 2013, 40, 20406-20414) reported that the combination of CdS composite TiO 2 nanoparticles and graphene can effectively improve the photocatalytic activity of TiO 2 , which can be applied to complex photoelectrodes and solar cells. , hydrogen production and other fields. Based on this background, the present invention synthesized a bismuth sulfide/titanium dioxide/graphene composite photocatalyst with high catalytic degradation activity under visible light.
发明内容Contents of the invention
本发明的目的：结合半导体复合、形貌改性和与石墨烯复合三种改性方法对原始TiO2进行深入改性，既可使其对光吸收拓展至可见光区域，增加可见光下催化效果；又可使TiO2呈颗粒状均匀分散在石墨烯层上，减少团聚，增加催化效果；还可增加对污染物的吸收、提高了载流子分离和转移效率，最终制备出在可见光下对有机污染物具有高催化降解活性的光催化剂。The purpose of the present invention is to combine the three modification methods of semiconductor compounding, shape modification and compounding with graphene to deeply modify the original TiO2 , which can extend the light absorption to the visible light region and increase the catalytic effect under visible light; It can also make TiO 2 evenly disperse on the graphene layer in the form of particles, reduce agglomeration, and increase the catalytic effect; it can also increase the absorption of pollutants, improve the carrier separation and transfer efficiency, and finally prepare organic carbon dioxide under visible light. Photocatalysts with high catalytic degradation activity for pollutants.
本发明的技术方案：一种在可见光下具有高催化降解活性的硫化铋/二氧化钛/石墨烯复合物的制法。按照以下步骤进行：The technical scheme of the present invention: a method for preparing a bismuth sulfide/titanium dioxide/graphene composite with high catalytic degradation activity under visible light. Follow the steps below:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中进行溶剂热反应，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温煅烧，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composite: Dissolve graphene oxide in 60mL of absolute ethanol at room temperature, continuously stir and ultrasonically disperse, add 0.0227g bismuth nitrate pentahydrate and 0.0186g nonahydrate under stirring Sodium sulfide, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; after stirring to obtain a uniform suspension Transfer to a polytetrafluoroethylene-lined high-pressure hydrothermal reaction kettle for solvothermal reaction. After the reaction, it is naturally cooled to room temperature. The obtained product is washed with deionized water and absolute ethanol three times in turn, and the obtained product is centrifuged. The sample was dried at 80°C for 8h, and then calcined under a nitrogen atmosphere at a heating rate of 4°C/min to finally obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了85％～198％和28％～74％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results show that, compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite is increased by 85%-198% and 28%-74%, respectively.
上述步骤(1)中，氧化石墨烯的量为10～200mg；氧化石墨烯超声分散时间为0.5～10h；钛酸四丁酯的加入量为4～8mL；溶剂热反应温度为160～200℃，溶剂热反应时间为18～30h；煅烧温度为450～600℃，煅烧时间为2～6h。In the above step (1), the amount of graphene oxide is 10-200mg; the ultrasonic dispersion time of graphene oxide is 0.5-10h; the addition amount of tetrabutyl titanate is 4-8mL; the solvothermal reaction temperature is 160-200°C , The solvothermal reaction time is 18~30h; the calcination temperature is 450~600°C, and the calcination time is 2~6h.
本发明采用简易的方法，即先经溶剂热再经煅烧处理合成了在可见光下具有高催化活性的硫化铋/二氧化钛/石墨烯复合物光催化剂。结果表明，硫化铋/TiO2可呈颗粒状均匀分布在石墨烯层表面，降低了TiO2在石墨烯层上的团聚，增强了TiO2与石墨烯间的相互作用，提高了光催化活性。The invention adopts a simple method, that is, the bismuth sulfide/titanium dioxide/graphene composite photocatalyst with high catalytic activity under visible light is synthesized through solvothermal and then calcined treatment. The results show that bismuth sulfide/TiO 2 can be evenly distributed on the surface of graphene layer in the form of particles, which reduces the agglomeration of TiO 2 on the graphene layer, enhances the interaction between TiO 2 and graphene, and improves the photocatalytic activity.
本发明的技术优点：硫化铋/二氧化钛/石墨烯复合物通过溶剂热一步法合成，再经煅烧处理，方法简单；通过硫化铋与石墨烯复合的协同作用，降低了TiO2的带隙，提高了其对有机污染物的吸附能力，增强了对可见光的利用率，降低了光生电子-空穴对的复合率，延长了载流子的寿命；同时硫化铋/TiO2纳米颗粒在石墨烯上均匀的附着，大大减少了TiO2团聚，提高了与石墨烯间的化学作用，从而极大地提高了复合物在可见光区域降解有机污染物的能力。The technical advantage of the present invention: bismuth sulfide/titanium dioxide/graphene compound is synthesized by solvothermal one-step method, and then through calcining treatment, the method is simple; Through the synergistic effect of bismuth sulfide and graphene compound, reduce the bandgap of TiO , improve It improves the adsorption capacity of organic pollutants, enhances the utilization rate of visible light, reduces the recombination rate of photogenerated electron-hole pairs, and prolongs the life of carriers; at the same time, bismuth sulfide/TiO 2 nanoparticles on graphene The uniform attachment greatly reduces TiO 2 agglomeration and improves the chemical interaction with graphene, thereby greatly improving the ability of the composite to degrade organic pollutants in the visible light region.
具体实施方式detailed description
下面实施例可以使本领域技术人员全面的理解本发明，但不以任何方式限制本发明。The following examples can enable those skilled in the art to fully understand the present invention, but do not limit the present invention in any way.
实施例1：Example 1:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将10mL氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散0.5h，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入4mL钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中160℃进行溶剂热反应18h，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温至450℃煅烧2h，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composite: Dissolve 10mL graphene oxide in 60mL absolute ethanol at room temperature, continuously stir, ultrasonically disperse for 0.5h, add 0.0227g bismuth nitrate pentahydrate and 0.0186 g sodium sulfide nonahydrate, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add 4 mL of tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; stir to obtain a uniform After the suspension was transferred to a polytetrafluoroethylene-lined high-pressure hydrothermal reactor at 160 ° C for solvothermal reaction for 18 hours, after the reaction was completed, it was naturally cooled to room temperature, and the obtained product was washed with deionized water and absolute ethanol in turn. Three times, the samples obtained by centrifugation were dried at 80°C for 8h, and then calcined at 450°C for 2h under a nitrogen atmosphere at a heating rate of 4°C/min to finally obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了103％和49％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results showed that compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite was increased by 103% and 49%, respectively.
实施例2：Example 2:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将10mL氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散4h，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入6mL钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中180℃进行溶剂热反应20h，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温至500℃煅烧4h，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composite: Dissolve 10mL graphene oxide in 60mL absolute ethanol at room temperature, continuously stir, ultrasonically disperse for 4h, add 0.0227g bismuth nitrate pentahydrate and 0.0186g Sodium sulfide nonahydrate, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add 6 mL of tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; stir to obtain a uniform The suspension was then transferred to a polytetrafluoroethylene-lined high-pressure hydrothermal reactor at 180°C for solvothermal reaction for 20 hours. After the reaction, it was naturally cooled to room temperature. The obtained product was washed with deionized water and absolute ethanol for 3 The second time, the sample obtained by centrifugation was dried at 80°C for 8h, and then calcined at 500°C for 4h at a rate of 4°C/min in a nitrogen atmosphere to finally obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了99％和45％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results showed that compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite was increased by 99% and 45%, respectively.
实施例3：Example 3:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将60mL氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散1h，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入4mL钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中200℃进行溶剂热反应30h，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温至600℃煅烧6h，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composite: Dissolve 60mL graphene oxide in 60mL absolute ethanol at room temperature, continuously stir, ultrasonically disperse for 1h, add 0.0227g bismuth nitrate pentahydrate and 0.0186g Sodium sulfide nonahydrate, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add 4 mL of tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; stir to obtain a uniform The suspension was then transferred to a polytetrafluoroethylene-lined high-pressure hydrothermal reactor at 200°C for solvothermal reaction for 30 hours. After the reaction, it was naturally cooled to room temperature. The obtained product was washed with deionized water and absolute ethanol for 3 The second time, the sample obtained by centrifugation was dried at 80°C for 8h, and then calcined at 600°C for 6h at a heating rate of 4°C/min under a nitrogen atmosphere to finally obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了98％和47％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results showed that compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite increased by 98% and 47%, respectively.
实施例4：Example 4:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将60mL氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散10h，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入8mL钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中160℃进行溶剂热反应24h，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温至500℃煅烧3h，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composite: Dissolve 60mL graphene oxide in 60mL absolute ethanol at room temperature, continuously stir, ultrasonically disperse for 10h, add 0.0227g bismuth nitrate pentahydrate and 0.0186g Sodium sulfide nonahydrate, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add 8 mL of tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; stir to obtain a uniform The suspension was then transferred to a polytetrafluoroethylene-lined high-pressure hydrothermal reactor at 160°C for solvothermal reaction for 24 hours. After the reaction, it was naturally cooled to room temperature. The obtained product was washed with deionized water and absolute ethanol for 3 The second time, the sample obtained by centrifugation was dried at 80°C for 8h, and then calcined at 500°C for 3h at a heating rate of 4°C/min under a nitrogen atmosphere to finally obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了195％和69％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results showed that compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite was increased by 195% and 69%, respectively.
实施例5：Example 5:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将100mL氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散6h，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入6mL钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中180℃进行溶剂热反应30h，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温至450℃煅烧3h，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composite: Dissolve 100mL graphene oxide in 60mL absolute ethanol at room temperature, continuously stir, ultrasonically disperse for 6h, add 0.0227g bismuth nitrate pentahydrate and 0.0186g Sodium sulfide nonahydrate, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add 6 mL of tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; stir to obtain a uniform The suspension was then transferred to a polytetrafluoroethylene-lined high-pressure hydrothermal reactor at 180°C for solvothermal reaction for 30 hours. After the reaction, it was naturally cooled to room temperature. The obtained product was washed with deionized water and absolute ethanol for 3 The second time, the sample obtained by centrifugation was dried at 80°C for 8h, and then calcined at 450°C for 3h under a nitrogen atmosphere at a heating rate of 4°C/min to obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了112％和48％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results showed that compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite was increased by 112% and 48%, respectively.
实施例6：Embodiment 6:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将100mL氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散1h，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入8mL钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中200℃进行溶剂热反应20h，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温至600℃煅烧4h，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composite: Dissolve 100mL graphene oxide in 60mL absolute ethanol at room temperature, continuously stir, ultrasonically disperse for 1h, add 0.0227g bismuth nitrate pentahydrate and 0.0186g Sodium sulfide nonahydrate, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add 8 mL of tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; stir to obtain a uniform The suspension was then transferred to a polytetrafluoroethylene-lined high-pressure hydrothermal reactor at 200°C for solvothermal reaction for 20 hours. After the reaction, it was naturally cooled to room temperature. The obtained product was washed with deionized water and absolute ethanol for 3 The second time, the sample obtained by centrifugation was dried at 80 °C for 8 h, and then calcined at 600 °C for 4 h at a heating rate of 4 °C/min in a nitrogen atmosphere to finally obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了142％和64％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results showed that compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite was increased by 142% and 64%, respectively.
实施例7：Embodiment 7:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将150mL氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散6h，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入6mL钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中160℃进行溶剂热反应26h，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温至450℃煅烧4h，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composites: Dissolve 150mL graphene oxide in 60mL absolute ethanol at room temperature, continuously stir, ultrasonically disperse for 6h, add 0.0227g bismuth nitrate pentahydrate and 0.0186g Sodium sulfide nonahydrate, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add 6 mL of tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; stir to obtain a uniform The suspension was then transferred to a polytetrafluoroethylene-lined high-pressure hydrothermal reactor at 160°C for solvothermal reaction for 26 hours. After the reaction, it was naturally cooled to room temperature. The obtained product was washed with deionized water and absolute ethanol for 3 The second time, the sample obtained by centrifugation was dried at 80°C for 8h, and then calcined at 450°C for 4h under a nitrogen atmosphere at a heating rate of 4°C/min to obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了105％和50％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results showed that compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite was increased by 105% and 50%, respectively.
实施例8：Embodiment 8:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将150mL氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散0.5h，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入4mL钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中180℃进行溶剂热反应24h，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温至500℃煅烧2h，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composite: Dissolve 150mL graphene oxide in 60mL absolute ethanol at room temperature, continuously stir, ultrasonically disperse for 0.5h, add 0.0227g bismuth nitrate pentahydrate and 0.0186 g sodium sulfide nonahydrate, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add 4 mL of tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; stir to obtain a uniform After the suspension was transferred to a polytetrafluoroethylene-lined high-pressure hydrothermal reactor at 180 ° C for solvothermal reaction for 24 hours, after the reaction was completed, it was naturally cooled to room temperature, and the obtained product was washed with deionized water and absolute ethanol in turn. Three times, the sample obtained by centrifugation was dried at 80°C for 8h, and then calcined at 500°C for 2h at a heating rate of 4°C/min under a nitrogen atmosphere to finally obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了85％和28％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results showed that compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite was increased by 85% and 28%, respectively.
实施例9：Embodiment 9:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将200mL氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散4h，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入8mL钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中160℃进行溶剂热反应26h，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温至600℃煅烧3h，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composite: Dissolve 200mL graphene oxide in 60mL absolute ethanol at room temperature, continuously stir, ultrasonically disperse for 4h, add 0.0227g bismuth nitrate pentahydrate and 0.0186g Sodium sulfide nonahydrate, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add 8 mL of tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; stir to obtain a uniform The suspension was then transferred to a polytetrafluoroethylene-lined high-pressure hydrothermal reactor at 160°C for solvothermal reaction for 26 hours. After the reaction, it was naturally cooled to room temperature. The obtained product was washed with deionized water and absolute ethanol for 3 The second time, the sample obtained by centrifugation was dried at 80 °C for 8 h, and then calcined at 600 °C for 3 h at a heating rate of 4 °C/min in a nitrogen atmosphere to finally obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了111％和49％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results showed that compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite was increased by 111% and 49%, respectively.
实施例10：Example 10:
(1)硫化铋/二氧化钛/石墨烯复合物的合成：在室温条件下将200mL氧化石墨烯溶解于60mL无水乙醇中连续搅拌、超声分散10h，搅拌下加入0.0227g五水硝酸铋和0.0186g九水硫化钠，继续搅拌30min得到均匀分散的悬浮液；然后，向上述悬浮液缓慢加入6mL钛酸四丁酯，并在连续搅拌的条件下滴加10mL水，继续搅拌1h；搅拌得到均匀的悬浮液后转移至含聚四氟乙烯内衬的高压水热反应釜中200℃进行溶剂热反应24h，反应结束后自然冷却至室温，得到的产品依次用去离子水、无水乙醇各洗涤3次，离心分离得到的样品在80℃下干燥8h，于氮气氛围下以4℃/min升温速率升温至450℃煅烧6h，最终得到硫化铋/二氧化钛/石墨烯复合物。为了对比，用类似的方法合成了TiO2纳米颗粒和硫化铋/TiO2。(1) Synthesis of bismuth sulfide/titanium dioxide/graphene composite: Dissolve 200mL graphene oxide in 60mL absolute ethanol at room temperature, continuously stir, ultrasonically disperse for 10h, add 0.0227g bismuth nitrate pentahydrate and 0.0186g Sodium sulfide nonahydrate, continue to stir for 30 minutes to obtain a uniformly dispersed suspension; then, slowly add 6 mL of tetrabutyl titanate to the above suspension, and add 10 mL of water dropwise under continuous stirring, and continue to stir for 1 hour; stir to obtain a uniform The suspension was then transferred to a polytetrafluoroethylene-lined high-pressure hydrothermal reactor at 200°C for solvothermal reaction for 24 hours. After the reaction, it was naturally cooled to room temperature. The obtained product was washed with deionized water and absolute ethanol for 3 The second time, the sample obtained by centrifugation was dried at 80 °C for 8 h, and then calcined at 450 °C for 6 h at a heating rate of 4 °C/min in a nitrogen atmosphere to finally obtain a bismuth sulfide/titanium dioxide/graphene composite. For comparison, TiO 2 nanoparticles and bismuth sulfide/TiO 2 were synthesized in a similar manner.
(2)硫化铋/二氧化钛/石墨烯复合物光降解有机污染物：将上述所制100mg光催化剂加入到500mL浓度为10mg/L的亚甲基蓝水溶液中，在黑暗中搅拌60min后于可见光下进行光催化降解实验，光降解时间持续90min，过程中每30min移取5mL溶液，离心后对上清液进行吸光度测量以计算降解效果。用同样的方法对TiO2纳米颗粒和硫化铋/TiO2进行催化降解效果检测。结果显示，相比TiO2纳米颗粒和硫化铋/TiO2，硫化铋/二氧化钛/石墨烯复合物的光催化降解率分别提高了114％和52％。(2) Photodegradation of organic pollutants by bismuth sulfide/titanium dioxide/graphene composites: Add 100 mg of the photocatalyst prepared above to 500 mL of methylene blue aqueous solution with a concentration of 10 mg/L, stir in the dark for 60 min, and then perform photocatalysis under visible light In the degradation experiment, the photodegradation time lasted 90 minutes, and 5 mL of the solution was pipetted every 30 minutes during the process. After centrifugation, the absorbance of the supernatant was measured to calculate the degradation effect. The same method was used to detect the catalytic degradation effect of TiO 2 nanoparticles and bismuth sulfide/TiO 2 . The results showed that compared with TiO 2 nanoparticles and bismuth sulfide/TiO 2 , the photocatalytic degradation rate of bismuth sulfide/titanium dioxide/graphene composite was increased by 114% and 52%, respectively.
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| CN107930617A (en) * | 2017-11-29 | 2018-04-20 | 江南大学 | A kind of witch culture TiO with high catalytic degradation activity2The preparation method of/graphene complex |
| CN107930616A (en) * | 2017-11-29 | 2018-04-20 | 江南大学 | A kind of preparation method of the molybdenum trioxide with high catalytic degradation activity/titanium dioxide/graphene compound |
| CN108144599A (en) * | 2017-12-25 | 2018-06-12 | 李雪琴 | A kind for the treatment of process of bismuthino composite photocatalyst for degrading dyeing waste water |
| CN109608055A (en) * | 2018-12-29 | 2019-04-12 | 河南科技大学 | A kind of bismuth sulfide sensitized titanium dioxide nanorod film and preparation method thereof |
| CN109608055B (en) * | 2018-12-29 | 2021-08-20 | 河南科技大学 | A kind of bismuth sulfide sensitized titanium dioxide nanorod film and preparation method thereof |
| CN111420685A (en) * | 2019-01-10 | 2020-07-17 | 欧阳峰 | FSBi-doped TiO for efficiently degrading acrylonitrile wastewater by sunlight catalysis2/SiO2Preparation and use of the catalyst |
| CN117920273A (en) * | 2023-12-05 | 2024-04-26 | 厦门斯研新材料技术有限公司 | Bimetallic deposited heterojunction photocatalytic composite material and preparation method thereof |
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