CN107876034A - A kind of Ti2O@TiO2Composite photo-catalyst and preparation method thereof - Google Patents
A kind of Ti2O@TiO2Composite photo-catalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 48
- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000012792 core layer Substances 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract 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 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 6
- 238000002441 X-ray diffraction Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000004298 light response Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000010586 diagram Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 238000001782 photodegradation Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 44
- 239000002994 raw material Substances 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910000048 titanium hydride Inorganic materials 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- -1 titanium hydride Chemical compound 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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Abstract
本发明公开了一种Ti2O@TiO2复合光催化剂及其制备方法，TiH2经过热处理不同温度和时间，逐步转化为Ti2O@TiO2复合材料，由于温度和时间的不同导致生成物比例不同。根据X射线衍射光谱（XRD)、复合样品的紫外‑可见吸收光谱图、不同样品的光催化降解亚甲基蓝分时图来分析得到了最佳的温度和时间参数。本发明的有益效果是使Ti2O/TiO2复合结构形成了一种核壳结构，可见光响应能力大大增强，减小了光生载流子的复合几率，促进光电转换效率，对光降解的速率也进一步增强，使其对亚甲基蓝等有机染料的降解速度得到大幅提升，制备工艺更加简单，大大节省了时间和成本。
The invention discloses a Ti 2 O@TiO 2 composite photocatalyst and a preparation method thereof. TiH 2 is gradually converted into a Ti 2 O@TiO 2 composite material through heat treatment at different temperatures and times. The proportions are different. According to X-ray diffraction spectrum (XRD), the ultraviolet-visible absorption spectrogram of composite sample, the photocatalytic degradation methylene blue time-sharing diagram of different samples is analyzed and obtained optimal temperature and time parameter. The beneficial effect of the present invention is that the Ti2O / TiO2 composite structure forms a core-shell structure, the visible light response ability is greatly enhanced, the recombination probability of photogenerated carriers is reduced, the photoelectric conversion efficiency is promoted, and the photodegradation rate is greatly improved. It is also further enhanced, so that the degradation speed of organic dyes such as methylene blue is greatly improved, and the preparation process is simpler, which greatly saves time and cost.
Description
技术领域technical field
本发明涉及纳米光催化材料技术领域，具体涉及一种Ti2O@TiO2复合光催化剂及其制备方法。The invention relates to the technical field of nano photocatalytic materials, in particular to a Ti2O @ TiO2 composite photocatalyst and a preparation method thereof.
背景技术Background technique
自从1972年日本科学家Fujishima和Honda发现在TiO2电极上可进行光催化分解水后，利用太阳能光催化越来越受到人们的关注。TiO2以其较高的光催化活性和化学稳定性以及无毒害、成本低等优点，被广泛应用于低成本薄膜太阳能电池和光催化剂的研究。目前，针对TiO2仅仅对紫外光吸收，对可见光无响应等缺点，开展对TiO2的进行金属/非金属掺杂、半导体/贵金属复合、调节晶面形貌等手段提高TiO2的光催化效率。寻找工艺简单、成本低廉、可见光响应的催化复合材料一直是研究的焦点。Since Japanese scientists Fujishima and Honda discovered in 1972 that photocatalytic water splitting can be carried out on TiO 2 electrodes, the use of solar photocatalysis has attracted more and more attention. TiO 2 is widely used in the research of low-cost thin-film solar cells and photocatalysts due to its high photocatalytic activity and chemical stability, non-toxicity and low cost. At present, in view of the shortcomings of TiO 2 that only absorbs ultraviolet light and has no response to visible light, the photocatalytic efficiency of TiO 2 is improved by means of metal/non-metal doping, semiconductor/noble metal compounding, and adjustment of crystal surface morphology. . Searching for catalytic composite materials with simple process, low cost and visible light response has always been the focus of research.
TiH2是一种工业原材料，一直应用于多孔铝合金、钛合金的制备。围绕TiH2的氧化做了很多研究工作。高洪武等研究了加热氧化处理对TiH2释氢行为的影响，证实在氧化过程中形成Ti xHOy、Ti2O3和TiO2多种相和结构。王耀奇等人也研究了氢化钛氧化处理及其热分解行为Ti2O3+TiO2 和Ti3O+TiO2]粉末冶金材料科学与工程20（2015）1-6]。诸多的氧化工作都是建立在以研究氧气氛充足和不断补充的条件下，没有实现低氧Ti2O和纯相Ti2O@TiO2复合材料制备。TiH 2 is an industrial raw material that has been used in the preparation of porous aluminum alloys and titanium alloys. Much research work has been done around the oxidation of TiH2 . Gao Hongwu et al. studied the effect of heating oxidation treatment on the hydrogen release behavior of TiH 2 , and confirmed that various phases and structures of Ti xHOy, Ti 2 O 3 and TiO 2 were formed during the oxidation process. Wang Yaoqi and others also studied the oxidation treatment of titanium hydride and its thermal decomposition behavior Ti 2 O 3 +TiO 2 and Ti 3 O+TiO 2 ] Powder Metallurgy Materials Science and Engineering 20 (2015) 1-6]. A lot of oxidation work is based on the condition of sufficient and continuous supplement of oxygen atmosphere, and the preparation of low-oxygen Ti 2 O and pure phase Ti 2 O@TiO 2 composites has not been realized.
发明内容Contents of the invention
本发明提出了一种限域空间氧化的方法，获得了一种新型Ti2O物相，形成Ti2O@TiO2复合光催化剂，解决了现有TiO2催化材料无法实现对可见光的吸收，光生电子易于复合，催化效率低下的问题。The present invention proposes a confined space oxidation method, obtains a new type of Ti 2 O phase, and forms a Ti 2 O@TiO 2 composite photocatalyst, which solves the problem that existing TiO 2 catalytic materials cannot absorb visible light. Photogenerated electrons are easy to recombine, and the catalytic efficiency is low.
为解决上述问题，本发明采用如下技术方案：一种Ti2O@TiO2复合光催化剂，Ti2O@TiO2复合光催化剂为核壳结构，壳层为TiO2，核层为Ti2O。In order to solve the above problems, the present invention adopts the following technical scheme: a Ti 2 O@TiO 2 composite photocatalyst, the Ti 2 O@TiO 2 composite photocatalyst has a core-shell structure, the shell layer is TiO 2 , and the core layer is Ti 2 O .
将TiH2球磨后置于密闭石英管内，高温煅烧得到Ti2O@TiO2复合光催化剂。TiH 2 is ball-milled and placed in a closed quartz tube, and calcined at high temperature to obtain Ti 2 O@TiO 2 composite photocatalyst.
所述TiH2球磨后粒径为2-6μm。The particle size of the TiH 2 after ball milling is 2-6 μm.
所述高温煅烧的温度为550-670℃，时间为2-10h。The temperature of the high-temperature calcination is 550-670° C., and the time is 2-10 hours.
所述每20g TiH2置于500mL的石英管内，容器内空气为一个大气压，与外界无气体交换。Each 20g of TiH 2 is placed in a 500mL quartz tube, the air in the container is at one atmospheric pressure, and there is no gas exchange with the outside world.
本发明的有益效果是：本发明制备的复合材料在400nm 以后可见光区域有明显增强。尤其是400-500 nm之间吸收强烈增强，电子结构分析表明，该材料的禁带类似金属材料，能够对可见光有效吸收，而且该吸收具有类SPR特征。Ti2O/TiO2光催化剂对光降解的速率增强，对亚甲基蓝等有机染料的降解速度得到大幅提升。形成的复合结构为原位氧化获得产物，界面结合良好，利于降低界面阻抗。相对于其他半导体复合、金属复合，原料成本低廉，TiH2是廉价工业原料。The beneficial effects of the invention are: the composite material prepared by the invention has obvious enhancement in the visible light region after 400nm. Especially the absorption between 400-500 nm is strongly enhanced, and the electronic structure analysis shows that the material's forbidden band is similar to that of metal materials, which can effectively absorb visible light, and the absorption has SPR-like characteristics. The photodegradation rate of Ti 2 O/TiO 2 photocatalyst is enhanced, and the degradation rate of organic dyes such as methylene blue is greatly improved. The formed composite structure is a product obtained by in-situ oxidation, and the interface is well bonded, which is beneficial to reduce the interface impedance. Compared with other semiconductor composites and metal composites, the cost of raw materials is low, and TiH 2 is a cheap industrial raw material.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention. Those skilled in the art can also obtain other drawings based on these drawings without creative work.
图1为本发明实施例1-7制备的材料的XRD图。Fig. 1 is an XRD pattern of materials prepared in Examples 1-7 of the present invention.
图2是复合材料的紫外-可见吸收光谱图。Fig. 2 is the ultraviolet-visible absorption spectrum diagram of the composite material.
图3是复合材料的光致发光谱（PL图谱）。Figure 3 is the photoluminescence spectrum (PL spectrum) of the composite material.
图4是不同条件下的复合样品光催化降解亚甲基蓝分解图。Figure 4 is the photocatalytic degradation of methylene blue decomposition diagrams of composite samples under different conditions.
图5是复合催化剂的高分辨TEM。Figure 5 is a high-resolution TEM of the composite catalyst.
具体实施方式Detailed ways
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
本实施例Ti2O@TiO2复合光催化剂为核壳结构，壳层为TiO2，核层为Ti2O，制备方法如下：The Ti 2 O@TiO 2 composite photocatalyst in this example has a core-shell structure, the shell layer is TiO 2 , and the core layer is Ti 2 O. The preparation method is as follows:
采用TiH2作为原材料，球磨TiH2得到2~6微米的颗粒，将20g球磨后的TiH2置于500ml密闭石英管内炉加热煅烧高温煅烧的温度为550℃，时间为6h，得到Ti2O@TiO2复合光催化剂。Use TiH 2 as raw material, ball mill TiH 2 to get 2~6 micron particles, put 20g of ball-milled TiH 2 in a 500ml closed quartz tube furnace for heating and calcining at a high temperature of 550°C for 6 hours to obtain Ti 2 O@ TiO2 composite photocatalyst.
实施例2Example 2
本实施例Ti2O@TiO2复合光催化剂为核壳结构，壳层为TiO2，核层为Ti2O，制备方法如下：The Ti 2 O@TiO 2 composite photocatalyst in this example has a core-shell structure, the shell layer is TiO 2 , and the core layer is Ti 2 O. The preparation method is as follows:
采用TiH2作为原材料，球磨TiH2得到2~6微米的颗粒，将20g球磨后的TiH2置于500ml密闭石英管内炉加热煅烧，容器内空气为一个大气压，与外界无气体交换，高温煅烧的温度为580℃，时间为2h，得到Ti2O@TiO2复合光催化剂。Use TiH 2 as raw material, ball mill TiH 2 to get 2~6 micron particles, put 20g of ball-milled TiH 2 in a 500ml closed quartz tube furnace for heating and calcining, the air in the container is at an atmospheric pressure, there is no gas exchange with the outside, high temperature calcined The temperature is 580° C., and the time is 2 hours to obtain a Ti 2 O@TiO 2 composite photocatalyst.
实施例3Example 3
本实施例Ti2O@TiO2复合光催化剂为核壳结构，壳层为TiO2，核层为Ti2O，制备方法如下：The Ti 2 O@TiO 2 composite photocatalyst in this example has a core-shell structure, the shell layer is TiO 2 , and the core layer is Ti 2 O. The preparation method is as follows:
采用TiH2作为原材料，球磨TiH2得到2~6微米的颗粒，将20g球磨后的TiH2置于500ml密闭石英管内炉加热煅烧，容器内空气为一个大气压，与外界无气体交换，高温煅烧的温度为580℃，时间为6h，得到Ti2O@TiO2复合光催化剂。Use TiH 2 as raw material, ball mill TiH 2 to get 2~6 micron particles, put 20g of ball-milled TiH 2 in a 500ml closed quartz tube furnace for heating and calcining, the air in the container is at an atmospheric pressure, there is no gas exchange with the outside, high temperature calcined The temperature is 580° C., and the time is 6 hours to obtain a Ti 2 O@TiO 2 composite photocatalyst.
实施例4Example 4
本实施例Ti2O@TiO2复合光催化剂为核壳结构，壳层为TiO2，核层为Ti2O，制备方法如下：The Ti 2 O@TiO 2 composite photocatalyst in this example has a core-shell structure, the shell layer is TiO 2 , and the core layer is Ti 2 O. The preparation method is as follows:
采用TiH2作为原材料，球磨TiH2得到2~6微米的颗粒，将20g球磨后的TiH2置于500ml密闭石英管内炉加热煅烧，容器内空气为一个大气压，与外界无气体交换，高温煅烧的温度为580℃，时间为10h，得到Ti2O@TiO2复合光催化剂。Use TiH 2 as raw material, ball mill TiH 2 to get 2~6 micron particles, put 20g of ball-milled TiH 2 in a 500ml closed quartz tube furnace for heating and calcining, the air in the container is at an atmospheric pressure, there is no gas exchange with the outside, high temperature calcined The temperature is 580° C., and the time is 10 h to obtain a Ti 2 O@TiO 2 composite photocatalyst.
实施例5Example 5
本实施例Ti2O@TiO2复合光催化剂为核壳结构，壳层为TiO2，核层为Ti2O，制备方法如下：The Ti 2 O@TiO 2 composite photocatalyst in this example has a core-shell structure, the shell layer is TiO 2 , and the core layer is Ti 2 O. The preparation method is as follows:
采用TiH2作为原材料，球磨TiH2得到2~6微米的颗粒，将20g球磨后的TiH2置于500ml密闭石英管内炉加热煅烧，容器内空气为一个大气压，与外界无气体交换，高温煅烧的温度为610℃，时间为6h，得到Ti2O@TiO2复合光催化剂。Use TiH 2 as raw material, ball mill TiH 2 to get 2~6 micron particles, put 20g of ball-milled TiH 2 in a 500ml closed quartz tube furnace for heating and calcining, the air in the container is at an atmospheric pressure, there is no gas exchange with the outside, high temperature calcined The temperature is 610° C., and the time is 6 hours to obtain a Ti 2 O@TiO 2 composite photocatalyst.
实施例6Example 6
本实施例Ti2O@TiO2复合光催化剂为核壳结构，壳层为TiO2，核层为Ti2O，制备方法如下：The Ti 2 O@TiO 2 composite photocatalyst in this example has a core-shell structure, the shell layer is TiO 2 , and the core layer is Ti 2 O. The preparation method is as follows:
采用TiH2作为原材料，球磨TiH2得到2~6微米的颗粒，将20g球磨后的TiH2置于500ml密闭石英管内炉加热煅烧，容器内空气为一个大气压，与外界无气体交换，高温煅烧的温度为640℃，时间为6h，得到Ti2O@TiO2复合光催化剂。Use TiH 2 as raw material, ball mill TiH 2 to get 2~6 micron particles, put 20g of ball-milled TiH 2 in a 500ml closed quartz tube furnace for heating and calcining, the air in the container is at an atmospheric pressure, there is no gas exchange with the outside, high temperature calcined The temperature is 640° C., and the time is 6 hours to obtain a Ti 2 O@TiO 2 composite photocatalyst.
实施例7Example 7
本实施例Ti2O@TiO2复合光催化剂为核壳结构，壳层为TiO2，核层为Ti2O，制备方法如下：The Ti 2 O@TiO 2 composite photocatalyst in this example has a core-shell structure, the shell layer is TiO 2 , and the core layer is Ti 2 O. The preparation method is as follows:
采用TiH2作为原材料，球磨TiH2得到2~6微米的颗粒，将20g球磨后的TiH2置于500ml密闭石英管内炉加热煅烧，容器内空气为一个大气压，与外界无气体交换，高温煅烧的温度为670℃，时间为10h，得到Ti2O@TiO2复合光催化剂。Use TiH 2 as raw material, ball mill TiH 2 to get 2~6 micron particles, put 20g of ball-milled TiH 2 in a 500ml closed quartz tube furnace for heating and calcining, the air in the container is at an atmospheric pressure, there is no gas exchange with the outside, high temperature calcined The temperature is 670° C., and the time is 10 h to obtain a Ti 2 O@TiO 2 composite photocatalyst.
如图1所示，为实施例1-7制备的Ti2O@TiO2复合光催化剂的XRD图，标准参考物相分别为TiO2,Ti2O和TiH2。从图中得到，在形同的加热时间（6h）内，随着加热温度的提高，Rutile-TiO2(R)相存在含量逐渐增加，Ti2O(T)相则在580℃以后逐渐减少，对于TiH2(TH)相，在550℃含量最大，当温度提升到580℃时含量急剧下降，在610℃和640℃时几乎不存在。TiH2在低温下稳定，达到某一温度后剧烈反应被氧化。As shown in Figure 1, it is the XRD pattern of the Ti 2 O@TiO 2 composite photocatalyst prepared in Examples 1-7, and the standard reference phases are TiO 2 , Ti 2 O and TiH 2 . It can be seen from the figure that within the same heating time (6h), as the heating temperature increases, the content of Rutile-TiO 2 (R) phase gradually increases, and the content of Ti 2 O(T) phase gradually decreases after 580°C , for the TiH 2 (TH) phase, the content is the largest at 550°C, the content drops sharply when the temperature rises to 580°C, and almost does not exist at 610°C and 640°C. TiH2 is stable at low temperature, and after reaching a certain temperature, it reacts vigorously and is oxidized.
各物质的物相比例如表1所示。The physical ratio of each substance is shown in Table 1, for example.
表1 实施例1-7催化剂中各物相比例。Table 1 The ratio of each phase in the catalysts of Examples 1-7.
图2说明了Ti2O相较于TiO2具有明显的可见光响应。一定量的Ti2O复合在400-500nm区域内形成有效的光吸收波段峰，且吸收峰值与Ti2O含量呈紧密相关的对应关系。可知Ti2O对于可见光的捕获能力较TiO2强。Figure 2 illustrates that Ti 2 O has a clear visible light response compared to TiO 2 . A certain amount of Ti 2 O is compounded to form an effective light absorption band peak in the 400-500nm region, and the absorption peak is closely related to the content of Ti 2 O. It can be seen that Ti 2 O has a stronger ability to capture visible light than TiO 2 .
图4是该催化剂降解有机物亚甲基蓝的降解曲线，从中得到纯金红石相的降解性能较差，捕获可见光的能力太小，低于10％。而Ti2O/TiO2复合相表现出更好的光催化性能，在610℃，6h时显示最好的光催化活性，说明了Ti2O/TiO2复合材料结构和可见光吸收，使光催化性能增强的主要原因，从而使降解率提高。同时，图3显示了，复合材料在光生载流子分离方面也有明显增强效果。Figure 4 is the degradation curve of the catalyst for degrading the organic methylene blue, from which the degradation performance of the pure rutile phase is poor, and the ability to capture visible light is too small, less than 10%. However, the Ti2O / TiO2 composite phase exhibited better photocatalytic performance, showing the best photocatalytic activity at 610 °C for 6 h, indicating that the Ti2O / TiO2 composite structure and visible light absorption make the photocatalytic The main reason for the performance enhancement, so that the degradation rate is improved. At the same time, Figure 3 shows that the composite material also has a significant enhancement effect on the separation of photogenerated carriers.
图5显示了Ti2O/TiO2复合光催化剂的图像，总体呈近规则颗粒状。透射电镜高分辨图像图像显示了其外层为金红石相的TiO2，内部为Ti2O。不同区域均有高分辨晶格图像作为依据。Figure 5 shows the image of the Ti2O / TiO2 composite photocatalyst, which is generally in the shape of near-regular particles. The high-resolution image of the transmission electron microscope shows that the outer layer is TiO 2 in the rutile phase, and the inner layer is Ti 2 O. Different regions are supported by high-resolution lattice images.
本发明通过TiH2氧化反应制备了一种独特的Ti2O/TiO2复合结构，Ti2O含量仅取决于热处理条件。以420 nm为中心的吸收光谱显示了复合材料的典型可见光响应，复合结构的形成和异质结有助于载流子分离。最优样品，可见光照射下 2 h，优化后的复合材料对亚甲基蓝水溶液的降解率为90%左右。The present invention prepares a unique Ti 2 O/TiO 2 composite structure through the TiH 2 oxidation reaction, and the Ti 2 O content only depends on the heat treatment conditions. The absorption spectrum centered at 420 nm shows the typical visible light response of the composite, and the formation of the composite structure and heterojunction facilitate the carrier separation. For the optimal sample, under visible light irradiation for 2 h, the degradation rate of the optimized composite material to methylene blue aqueous solution is about 90%.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of the present invention. within the scope of protection.
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