CN101559368B - Visible light active boron-nickel co-doped titanium dioxide solid solution catalyst and preparation method thereof - Google Patents
Visible light active boron-nickel co-doped titanium dioxide solid solution catalyst and preparation method thereof 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 126
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 50
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 239000006104 solid solution Substances 0.000 title abstract description 38
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 20
- 229910052796 boron Inorganic materials 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 90
- 239000012153 distilled water Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000011941 photocatalyst Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000006199 nebulizer Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 238000005118 spray pyrolysis Methods 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims 4
- 238000005406 washing Methods 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 10
- 239000007921 spray Substances 0.000 abstract description 8
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- 230000000694 effects Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 10
- -1 nitrogen-containing compound Chemical class 0.000 description 9
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 238000011160 research Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000003933 environmental pollution control Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及一种可见光活性硼镍共掺杂二氧化钛固溶体催化剂及制备方法，属于湿法化学制造纳米材料领域。The invention relates to a visible-light active boron-nickel co-doped titanium dioxide solid solution catalyst and a preparation method, belonging to the field of wet chemical manufacturing of nanometer materials.
背景技术Background technique
近年来，作为一种廉价、稳定、无毒、催化性能良好的光催化剂，TiO2成为了光催化技术领域研究的热点。但是由于TiO2带隙较宽(3.0～3.2eV)，只能被387nm以下紫外光激发，不能充分利用太阳能，且光催化反应效率不高，限制了其现实应用。为了扩展TiO2对可见光的响应，提高利用太阳光的效率，人们对TiO2光催化剂进行了大量的改性研究，例如采用染料敏化、贵金属沉积、半导体复合、金属离子和非金属离子掺杂等方法。其中，对TiO2掺杂改性是提高其可见光催化能力最主要手段。前期研究多集中在金属离子(Fe、Co、Ni、La等)掺杂，但是引入金属离子容易形成载流子复合中心，降低光催化效率，而且催化剂稳定性不高。随后，由于非金属离子(S、N、C、I等)掺杂能取代TiO2中的部分O原子，使半导体的价带位置升高，缩小半导体禁带宽度，使其吸收带边红移而提高其在可见光区的催化活性，从而成为研究的热点。除了对TiO2进行单一元素的掺杂，近几年，纳米TiO2共掺杂正日益成为TiO2光催化领域的研究热点，具有很好的研究价值和前景。不少研究者对共掺杂TiO2进行了研究，结果表明，当掺杂的元素合适时，可在TiO2的禁带中引入掺杂能级，使其禁带窄化，能量较小的光子可以激发电子发生跃迁，即能吸收波长较长的光，光吸收带边红移，扩宽了光响应范围，提高了量子效率，从而有助于光催化效率的提高。如S-N、B-S等的共掺杂在单掺杂的基础上，光吸收红移程度进一步加大，可见光响应增强；N与Fe、La和Ta等共掺杂可产生协同作用，进一步提高光响应范围和光催化活性；Zr掺杂TiO2能显著提高光催化剂的催化能力。关于B和Ni共掺杂TiO2光催化剂的研究尚未见文献报道。In recent years, as a cheap, stable, non-toxic and good catalytic photocatalyst, TiO2 has become a research hotspot in the field of photocatalytic technology. However, due to the wide band gap (3.0-3.2eV) of TiO 2 , it can only be excited by ultraviolet light below 387nm, which cannot make full use of solar energy, and the photocatalytic reaction efficiency is not high, which limits its practical application. In order to expand the response of TiO2 to visible light and improve the efficiency of utilizing sunlight, a lot of researches have been done on the modification of TiO2 photocatalysts, such as dye sensitization, noble metal deposition, semiconductor recombination, metal ion and non-metal ion doping and other methods. Among them, the doping modification of TiO2 is the most important means to improve its visible light catalytic ability. Previous studies mostly focused on the doping of metal ions (Fe, Co, Ni, La, etc.), but the introduction of metal ions is easy to form a carrier recombination center, which reduces the photocatalytic efficiency and the stability of the catalyst is not high. Subsequently, due to the doping of non-metal ions (S, N, C, I, etc.) to replace some of the O atoms in TiO 2 , the valence band position of the semiconductor is raised, the forbidden band width of the semiconductor is narrowed, and the absorption band edge is red-shifted. And improving its catalytic activity in the visible light region has become a research hotspot. In addition to doping TiO 2 with a single element, nano-TiO 2 co-doping has increasingly become a research hotspot in the field of TiO 2 photocatalysis in recent years, which has good research value and prospects. Many researchers have studied co-doped TiO 2 , and the results show that when the doped elements are suitable, doping energy levels can be introduced into the forbidden band of TiO 2 to narrow the forbidden band, and the smaller energy Photons can excite electrons to make transitions, that is, they can absorb light with longer wavelengths, and the light absorption band edge is red-shifted, which broadens the photoresponse range and improves the quantum efficiency, thus contributing to the improvement of photocatalytic efficiency. For example, the co-doping of SN, BS, etc., on the basis of single doping, further increases the red shift of light absorption and enhances the visible light response; co-doping of N and Fe, La, and Ta can produce synergistic effects and further improve the photoresponse Range and photocatalytic activity; Zr-doped TiO2 can significantly improve the catalytic ability of photocatalysts. The research on B and Ni co-doped TiO2 photocatalysts has not been reported in the literature.
目前尚未见到关于硼镍共掺杂二氧化钛催化剂制备的专利报道，国内关于涉及共掺杂TiO2催化剂的专利仅限于制备N-In共掺杂、N-S共掺杂、N-Sn共掺杂。如以钛酸酯为前躯体，以含氮化合物、铟盐为掺杂剂，采用水解沉淀法制备锐钛矿相和金红石相混晶的纳米N-In共掺杂光催化剂(申请号为200710059504.0，公开号为CN101130160)；以钛酸酯为前躯体，以含氮化合物、锡盐为掺杂剂，用水解沉淀法制备锐钛矿相的纳米光催化剂(申请号为200710057891，公开号为101108336)；通过水解沉淀法制备氮和硫双组分掺杂型的纳米二氧化钛(申请号为200610040382，公开号为1850618)。At present, there is no patent report on the preparation of boron-nickel co-doped titania catalysts. Domestic patents related to co-doped TiO 2 catalysts are limited to the preparation of N-In co-doping, NS co-doping, and N-Sn co-doping. For example, using titanate as a precursor, nitrogen-containing compounds and indium salts as dopants, a nano-N-In co-doped photocatalyst with mixed crystals of anatase phase and rutile phase was prepared by hydrolysis precipitation (application number is 200710059504.0 , the publication number is CN101130160); with titanate as precursor, nitrogen-containing compound and tin salt as dopant, the nano-photocatalyst of anatase phase is prepared by hydrolytic precipitation (application number is 200710057891, publication number is 101108336 ); prepare nitrogen and sulfur two-component doped nano-titanium dioxide by hydrolysis precipitation method (application number is 200610040382, publication number is 1850618).
本发明利用喷雾热解法制备硼镍共掺杂二氧化钛固溶体催化剂材料，该材料具有很高的可见光光催化活性，在环境污染治理领域有很大的应用潜力；本发明工艺简单，条件易控，对设备要求较低，便于进一步扩大化生产。The invention utilizes a spray pyrolysis method to prepare a boron-nickel co-doped titanium dioxide solid solution catalyst material, the material has high visible light photocatalytic activity, and has great application potential in the field of environmental pollution control; the invention has simple process and easy controllable conditions, The requirements for equipment are low, which is convenient for further expanding production.
发明内容Contents of the invention
本发明的目的在于提供一种采用喷雾热解法合成硼镍共掺杂二氧化钛固溶体光催化材料及制备方法，该硼镍共掺杂二氧化钛材料具有很好的可见光响应光催化性能。The object of the present invention is to provide a boron-nickel co-doped titanium dioxide solid solution photocatalytic material synthesized by a spray pyrolysis method and a preparation method thereof. The boron-nickel co-doped titanium dioxide material has good visible light-responsive photocatalytic performance.
实现上述目的的一种硼镍共掺杂二氧化钛光催化剂，其特征在于：以四氯化钛为前躯体，以含硼化合物、镍盐为掺杂剂，用喷雾热解法制备锐钛矿相的B-Ni共掺杂TiO2光催化剂，该催化剂组成以质量百分率计，B的含量为0.99％，Ni的含量为0.7％，其余为TiO2。该催化剂为直径在0.5～10μm范围内的微米球。A boron-nickel co-doped titanium dioxide photocatalyst for achieving the above-mentioned purpose is characterized in that: anatase phase is prepared by spray pyrolysis method with titanium tetrachloride as precursor, boron-containing compound and nickel salt as dopant B-Ni co-doped TiO 2 photocatalyst, the catalyst is composed of 0.99% B content, 0.7% Ni content and the rest is TiO 2 in terms of mass percentage. The catalyst is a microsphere with a diameter in the range of 0.5-10 μm.
所述的硼镍共掺杂二氧化钛光催化剂的制备方法，其制备步骤为：The preparation method of described boron-nickel co-doped titanium dioxide photocatalyst, its preparation steps are:
步骤1、采用四氯化钛为原材料，在搅拌的条件下，用4℃蒸馏水配置成四氯化钛溶液，溶液中钛离子的含量为5-20mmol/L；Step 1. Using titanium tetrachloride as the raw material, under stirring conditions, use distilled water at 4°C to prepare a titanium tetrachloride solution, the content of titanium ions in the solution is 5-20mmol/L;
步骤2、在另一容器中，用4℃蒸馏水配置含硼化合物和二价镍盐溶液，溶液中可溶性含硼化合物的含量为5-20mmol/L，溶液中镍离子的含量为0.5-2mmol/L，且溶液中硼化合物的摩尔含量为镍离子的摩尔含量的10倍，所述的可溶性含硼化合物为硼酸或硼氢化钠；Step 2. In another container, prepare boron-containing compound and divalent nickel salt solution with 4°C distilled water. The content of soluble boron-containing compound in the solution is 5-20mmol/L, and the content of nickel ion in the solution is 0.5-2mmol/L L, and the molar content of boron compound in the solution is 10 times of the molar content of nickel ion, and described soluble boron-containing compound is boric acid or sodium borohydride;
步骤3、在步骤1所得的溶液处于搅拌的条件下，将步骤2所得的溶液倒入步骤1所得的溶液中，两种溶液的体积比为1∶1，钛离子摩尔浓度与含硼化合物摩尔浓度相等；Step 3, under the condition that the solution obtained in step 1 is under agitation, pour the solution obtained in step 2 into the solution obtained in step 1, the volume ratio of the two solutions is 1: 1, the molar concentration of titanium ions is equal to the molar concentration of boron-containing compound Concentration is equal;
步骤4、将步骤3所得的溶液倒入超声喷雾器的容器中，在500～700℃空气气氛中喷雾热解，反应0.5～2小时；Step 4. Pour the solution obtained in step 3 into a container of an ultrasonic nebulizer, spray and pyrolyze it in an air atmosphere at 500-700°C, and react for 0.5-2 hours;
步骤5、在步骤4的反应过程结束后，将固体产物过滤，并用蒸馏水或乙醇淋洗产物3次以上；
步骤6、将步骤5的产物在50℃下干燥3～10小时，即可得到淡黄色的硼镍共掺杂二氧化钛光催化剂材料。Step 6. Dry the product of
本发明的硼镍共掺杂二氧化钛的制备方法中，所述的二价镍盐为硫酸镍，氯化镍或硝酸镍。In the preparation method of boron-nickel co-doped titanium dioxide of the present invention, the divalent nickel salt is nickel sulfate, nickel chloride or nickel nitrate.
本发明的优点：Advantages of the present invention:
1、合成路线简单，对设备要求较低，整个工艺过程容易控制，符合实际生产的需要；1. The synthesis route is simple, the requirements for equipment are low, the whole process is easy to control, and it meets the needs of actual production;
2、合成的硼镍共掺杂二氧化钛固溶体材料纯度高，颗粒尺寸大小均匀，分散性好；2. The synthesized boron-nickel co-doped titanium dioxide solid solution material has high purity, uniform particle size and good dispersion;
3、硼镍共掺杂二氧化钛固溶体材料具有很高的可见光光催化活性，在环境污染治理领域有很大的应用潜力。3. Boron-nickel co-doped titanium dioxide solid solution material has high visible light photocatalytic activity, and has great application potential in the field of environmental pollution control.
附图说明Description of drawings
图1是本发明制备的硼镍共掺杂二氧化钛固溶体的1万倍放大的扫描电子显微镜图Fig. 1 is the 10,000 times enlarged scanning electron microscope picture of the boron-nickel co-doped titanium dioxide solid solution prepared by the present invention
图2是本发明制备的硼镍共掺杂二氧化钛固溶体的3万倍放大的扫描电子显微镜图Fig. 2 is the 30,000 times enlarged scanning electron micrograph of the boron-nickel co-doped titanium dioxide solid solution prepared by the present invention
图3是本发明制备的硼镍共掺杂二氧化钛固溶体的XRD图Fig. 3 is the XRD figure of the boron-nickel co-doped titanium dioxide solid solution prepared by the present invention
图4是本发明制备的硼镍共掺杂二氧化钛固溶体的XPS图Fig. 4 is the XPS figure of the boron-nickel co-doped titanium dioxide solid solution prepared by the present invention
图5是本发明制备的硼镍共掺杂二氧化钛固溶体在模拟太阳光作用下的NO气体降解-时间曲线Fig. 5 is the NO gas degradation-time curve of the boron-nickel co-doped titanium dioxide solid solution prepared by the present invention under the action of simulated sunlight
所得硼镍共掺杂二氧化钛固溶体经过扫描电子显微镜图(JSM-5600)1万倍放大下观察(见图1)，硼镍共掺杂二氧化钛固溶体由直径在0.5～10μm的微球组成，有较好的纯度。扫描电子显微镜3万倍放大下的观察结果(见图2)说明二氧化钛固溶体微球为空心结构。所得硼镍共掺杂二氧化钛固溶体样品经XRD测试，衍射图谱中(见图3)的特征峰与二氧化钛标准衍射图谱(TiO2 JCPDS 84-1285)的峰值吻合。所得硼镍共掺杂二氧化钛固溶体样品经XPS测试，XPS谱(见图4)说明硼和镍成功掺杂在二氧化钛晶格中，其中B的质量含量为0.99％，Ni的质量含量为0.7％，其余为TiO2。所得硼镍共掺杂二氧化钛固溶体催化剂在模拟太阳光作用下降解初始浓度为400ppb的NO气体，降解-时间曲线(见图5)说明硼镍共掺杂二氧化钛固溶体催化剂有很好的可见光响应光催化活性。The resulting boron-nickel co-doped titanium dioxide solid solution was observed under a scanning electron microscope (JSM-5600) at 10,000 times magnification (see Figure 1), and the boron-nickel co-doped titanium dioxide solid solution was composed of microspheres with a diameter of 0.5-10 μm. good purity. The observation results under 30,000 times magnification of the scanning electron microscope (see Figure 2) show that the titanium dioxide solid solution microspheres have a hollow structure. The resulting boron-nickel co-doped titanium dioxide solid solution sample was tested by XRD, and the characteristic peaks in the diffraction pattern (see Figure 3) coincided with the peaks of the titanium dioxide standard diffraction pattern (TiO 2 JCPDS 84-1285). Gained boron-nickel co-doped titania solid solution sample is tested by XPS, and XPS spectrum (see Figure 4) shows that boron and nickel are successfully doped in the titania lattice, wherein the mass content of B is 0.99%, and the mass content of Ni is 0.7%, The remainder is TiO 2 . The obtained boron-nickel co-doped titanium dioxide solid solution catalyst degrades NO gas with an initial concentration of 400ppb under the action of simulated sunlight, and the degradation-time curve (see Figure 5) shows that the boron-nickel co-doped titanium dioxide solid solution catalyst has a good visible light response photocatalysis active.
具体实施方式Detailed ways
实施例1Example 1
制备硼镍共掺杂二氧化钛固溶体光催化剂，制备步骤为：Preparation of boron-nickel co-doped titanium dioxide solid solution photocatalyst, the preparation steps are:
步骤1、采用四氯化钛为原材料，在搅拌的条件下，用4℃蒸馏水配置成四氯化钛溶液，溶液中钛离子的含量为5mmol/L；Step 1, using titanium tetrachloride as the raw material, under the condition of stirring, use distilled water at 4°C to prepare a titanium tetrachloride solution, the content of titanium ions in the solution is 5 mmol/L;
步骤2、在另一容器中，用4℃蒸馏水配置硼酸和氯化镍溶液，溶液中硼酸的含量为5mmol/L；溶液中氯化镍的含量为0.5mmol/L；Step 2, in another container, configure boric acid and nickel chloride solution with 4°C distilled water, the content of boric acid in the solution is 5mmol/L; the content of nickel chloride in the solution is 0.5mmol/L;
步骤3、在步骤1所得的溶液处于搅拌的条件下，将步骤2所得的溶液倒入步骤1所得的溶液中，两种溶液的体积比为1∶1；Step 3, under the condition that the solution obtained in step 1 is under stirring, pour the solution obtained in step 2 into the solution obtained in step 1, and the volume ratio of the two solutions is 1:1;
步骤4、在步骤3所得的溶液倒入超声喷雾器的容器中，在500℃空气气氛中喷雾热解，反应1小时；Step 4. Pour the solution obtained in step 3 into a container of an ultrasonic nebulizer, spray and pyrolyze it in an air atmosphere at 500°C, and react for 1 hour;
步骤5、在步骤4的反应过程结束后，将固体产物过滤，并用蒸馏水或乙醇3次淋洗产物；
步骤6、将步骤5的产物在50℃下干燥3小时，即可得到淡黄色的硼镍共掺杂二氧化钛固溶体光催化剂材料。Step 6. Dry the product of
所得硼镍共掺杂二氧化钛固溶体光催化剂材料经过扫描电子显微镜图(JSM-5600)1万倍放大下观察(见图1)，硼镍共掺杂二氧化钛由直径在0.5～10μm的微球组成，有较好的纯度。扫描电子显微镜3万倍放大下的观察结果(见图2)说明二氧化钛固溶体微球为空心结构。所得硼镍共掺杂二氧化钛固溶体样品经XRD测试，衍射图谱中(见图3)的特征峰与二氧化钛标准衍射图谱(TiO2 JCPDS 84-1285)的峰值吻合。所得硼镍共掺杂二氧化钛样品经XPS测试，XPS谱(见图4)说明硼和镍成功掺杂在二氧化钛晶格中。其中B的质量含量为0.99％，Ni的质量含量为0.7％，其余为TiO2。所得硼镍共掺杂二氧化钛固溶体催化剂在模拟太阳光作用下降解初始浓度为400ppb的NO气体，降解-时间曲线(见图5)说明硼镍共掺杂二氧化钛固溶体光催化剂有很好的可见光响应光催化活性。The obtained boron-nickel co-doped titanium dioxide solid solution photocatalyst material was observed under a scanning electron microscope (JSM-5600) at 10,000 times magnification (see Figure 1). The boron-nickel co-doped titanium dioxide was composed of microspheres with a diameter of 0.5-10 μm. Has better purity. The observation results under 30,000 times magnification of the scanning electron microscope (see Figure 2) show that the titanium dioxide solid solution microspheres have a hollow structure. The resulting boron-nickel co-doped titanium dioxide solid solution sample was tested by XRD, and the characteristic peaks in the diffraction pattern (see Figure 3) coincided with the peaks of the titanium dioxide standard diffraction pattern (TiO 2 JCPDS 84-1285). The obtained boron-nickel co-doped titania sample was tested by XPS, and the XPS spectrum (see FIG. 4 ) indicated that boron and nickel were successfully doped in the titania lattice. The mass content of B is 0.99%, the mass content of Ni is 0.7%, and the rest is TiO 2 . The obtained boron-nickel co-doped titanium dioxide solid solution catalyst degrades NO gas with an initial concentration of 400ppb under the action of simulated sunlight, and the degradation-time curve (see Figure 5) shows that the boron-nickel co-doped titanium dioxide solid solution photocatalyst has good visible light response light catalytic activity.
实施例2Example 2
制备硼镍共掺杂二氧化钛固溶体光催化剂，制备步骤为：Preparation of boron-nickel co-doped titanium dioxide solid solution photocatalyst, the preparation steps are:
步骤1、采用四氯化钛为原材料，在搅拌的条件下，用4℃蒸馏水配置成四氯化钛溶液，溶液中钛离子的含量为20mmol/L；Step 1, using titanium tetrachloride as the raw material, under the condition of stirring, use distilled water at 4°C to prepare a titanium tetrachloride solution, the content of titanium ions in the solution is 20mmol/L;
步骤2、在另一容器中，用4℃蒸馏水配置硼酸和氯化镍溶液，溶液中硼酸的含量为20mmol/L；溶液中氯化镍的含量为2mmol/L；Step 2, in another container, configure boric acid and nickel chloride solution with 4°C distilled water, the content of boric acid in the solution is 20mmol/L; the content of nickel chloride in the solution is 2mmol/L;
步骤3、在步骤1所得的溶液处于搅拌的条件下，将步骤2所得的溶液倒入步骤1所得的溶液中，两种溶液的体积比为1∶1；Step 3, under the condition that the solution obtained in step 1 is under stirring, pour the solution obtained in step 2 into the solution obtained in step 1, and the volume ratio of the two solutions is 1:1;
步骤4、在步骤3所得的溶液倒入超声喷雾器的容器中，在600℃空气气氛中喷雾热解，反应2小时；Step 4. Pour the solution obtained in step 3 into a container of an ultrasonic nebulizer, spray and pyrolyze it in an air atmosphere at 600°C, and react for 2 hours;
步骤5、在步骤4的反应过程结束后，将固体产物过滤，并用蒸馏水或乙醇4次淋洗产物；
步骤6、将步骤5的产物在50℃下干燥10小时，即得到淡黄色的硼镍共掺杂二氧化钛固溶体光催化剂材料。Step 6. Dry the product of
实施例3Example 3
制备硼镍共掺杂二氧化钛固溶体光催化剂，制备步骤为：Preparation of boron-nickel co-doped titanium dioxide solid solution photocatalyst, the preparation steps are:
步骤1、采用四氯化钛为原材料，在搅拌的条件下，用4℃蒸馏水配置成四氯化钛溶液，溶液中钛离子的含量为10mmol/L；Step 1, using titanium tetrachloride as the raw material, under the condition of stirring, use distilled water at 4°C to prepare a titanium tetrachloride solution, the content of titanium ions in the solution is 10mmol/L;
步骤2、在另一容器中，用4℃蒸馏水配置硼氢化钠和硫酸镍溶液，溶液中硼氢化钠的含量为10mmol/L；溶液中硫酸镍的含量为1mmol/L；Step 2. In another container, configure sodium borohydride and nickel sulfate solutions with 4°C distilled water. The content of sodium borohydride in the solution is 10mmol/L; the content of nickel sulfate in the solution is 1mmol/L;
步骤3、在步骤1所得的溶液处于搅拌的条件下，将步骤2所得的溶液倒入步骤1所得的溶液中，两种溶液的体积比为1∶1；Step 3, under the condition that the solution obtained in step 1 is under stirring, pour the solution obtained in step 2 into the solution obtained in step 1, and the volume ratio of the two solutions is 1:1;
步骤4、在步骤3所得的溶液倒入超声喷雾器的容器中，在700℃空气气氛中喷雾热解，反应0.5小时；Step 4. Pour the solution obtained in step 3 into a container of an ultrasonic nebulizer, spray and pyrolyze it in an air atmosphere at 700°C, and react for 0.5 hours;
步骤5、在步骤4的反应过程结束后，将固体产物过滤，并用蒸馏水或乙醇3次淋洗产物；
步骤6、将步骤5的产物在50℃下干燥5小时，即得到淡黄色的硼镍共掺杂二氧化钛固溶体光催化剂材料。Step 6. Dry the product of
实施例4Example 4
制备硼镍共掺杂二氧化钛固溶体光催化剂，制备步骤为：Preparation of boron-nickel co-doped titanium dioxide solid solution photocatalyst, the preparation steps are:
步骤1、采用四氯化钛为原材料，在搅拌的条件下，用4℃蒸馏水配置成四氯化钛溶液，溶液中钛离子的含量为20mmol/L；Step 1, using titanium tetrachloride as the raw material, under the condition of stirring, use distilled water at 4°C to prepare a titanium tetrachloride solution, the content of titanium ions in the solution is 20mmol/L;
步骤2、在另一容器中，用4℃蒸馏水配置硼氢化钠和硫酸镍溶液，溶液中硼氢化钠的含量为20mmol/L；溶液中硫酸镍的含量为2mmol/L；Step 2. In another container, configure sodium borohydride and nickel sulfate solutions with 4°C distilled water. The content of sodium borohydride in the solution is 20mmol/L; the content of nickel sulfate in the solution is 2mmol/L;
步骤3、在步骤1所得的溶液处于搅拌的条件下，将步骤2所得的溶液倒入步骤1所得的溶液中，两种溶液的体积比为1∶1；Step 3, under the condition that the solution obtained in step 1 is under stirring, pour the solution obtained in step 2 into the solution obtained in step 1, and the volume ratio of the two solutions is 1:1;
步骤4、在步骤3所得的溶液倒入超声喷雾器的容器中，在700℃空气气氛中喷雾热解，反应2小时；Step 4. Pour the solution obtained in step 3 into a container of an ultrasonic nebulizer, spray and pyrolyze it in an air atmosphere at 700°C, and react for 2 hours;
步骤5、在步骤4的反应过程结束后，将固体产物过滤，并用蒸馏水或乙醇4次淋洗产物；
步骤6、将步骤5的产物在50℃下干燥10小时，即得到淡黄色的硼镍共掺杂二氧化钛固溶体光催化剂材料。Step 6. Dry the product of
实施例5Example 5
制备硼镍共掺杂二氧化钛固溶体光催化剂，制备步骤为：Preparation of boron-nickel co-doped titanium dioxide solid solution photocatalyst, the preparation steps are:
步骤1、采用四氯化钛为原材料，在搅拌的条件下，用4℃蒸馏水配置成四氯化钛溶液，溶液中钛离子的含量为5mmol/L；Step 1, using titanium tetrachloride as the raw material, under the condition of stirring, use distilled water at 4°C to prepare a titanium tetrachloride solution, the content of titanium ions in the solution is 5 mmol/L;
步骤2、在另一容器中，用4℃蒸馏水配置硼酸和硝酸镍溶液，溶液中硼酸的含量为5mmol/L；溶液中镍离子的含量为0.5mmol/L；Step 2, in another container, configure boric acid and nickel nitrate solution with 4°C distilled water, the content of boric acid in the solution is 5mmol/L; the content of nickel ions in the solution is 0.5mmol/L;
步骤3、在步骤1所得的溶液处于搅拌的条件下，将步骤2所得的溶液倒入步骤1所得的溶液中，两种溶液的体积比为1∶1；Step 3, under the condition that the solution obtained in step 1 is under stirring, pour the solution obtained in step 2 into the solution obtained in step 1, and the volume ratio of the two solutions is 1:1;
步骤4、在步骤3所得的溶液倒入超声喷雾器的容器中，在600℃空气气氛中喷雾热解，反应2小时；Step 4. Pour the solution obtained in step 3 into a container of an ultrasonic nebulizer, spray and pyrolyze it in an air atmosphere at 600°C, and react for 2 hours;
步骤5、在步骤4的反应过程结束后，将固体产物过滤，并用蒸馏水或乙醇4次淋洗产物；
步骤6、将步骤5的产物在50℃下干燥5小时，即得到淡黄色的硼镍共掺杂二氧化钛固溶体光催化剂材料。Step 6. Dry the product of
实施例6Example 6
制备硼镍共掺杂二氧化钛固溶体光催化剂，制备步骤为：Preparation of boron-nickel co-doped titanium dioxide solid solution photocatalyst, the preparation steps are:
步骤1、采用四氯化钛为原材料，在搅拌的条件下，用4℃蒸馏水配置成四氯化钛溶液，溶液中钛离子的含量为20mmol/L；Step 1, using titanium tetrachloride as the raw material, under the condition of stirring, use distilled water at 4°C to prepare a titanium tetrachloride solution, the content of titanium ions in the solution is 20mmol/L;
步骤2、在另一容器中，用4℃蒸馏水配置硼氢化钠和硝酸镍溶液，溶液中硼氢化钠的含量为20mmol/L；溶液中镍离子的含量为2mmol/L；Step 2. In another container, configure sodium borohydride and nickel nitrate solutions with 4°C distilled water. The content of sodium borohydride in the solution is 20mmol/L; the content of nickel ions in the solution is 2mmol/L;
步骤3、在步骤1所得的溶液处于搅拌的条件下，将步骤2所得的溶液倒入步骤1所得的溶液中，两种溶液的体积比为1∶1；Step 3, under the condition that the solution obtained in step 1 is under stirring, pour the solution obtained in step 2 into the solution obtained in step 1, and the volume ratio of the two solutions is 1:1;
步骤4、在步骤3所得的溶液倒入超声喷雾器的容器中，在700℃空气气氛中喷雾热解，反应2小时；Step 4. Pour the solution obtained in step 3 into a container of an ultrasonic nebulizer, spray and pyrolyze it in an air atmosphere at 700°C, and react for 2 hours;
步骤5、在步骤4的反应过程结束后，将固体产物过滤，并用蒸馏水或乙醇3次淋洗产物；
步骤6、将步骤5的产物在50℃下干燥3小时，即得到淡黄色的硼镍共掺杂二氧化钛固溶体光催化剂材料。Step 6. Dry the product of
实施例2～6所得样品的组成、形貌、结构、XPS谱及降解NO气体的降解-时间曲线与实施例1相同。The composition, morphology, structure, XPS spectrum and degradation-time curve of degrading NO gas of the samples obtained in Examples 2-6 are the same as those in Example 1.
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