CN110124666A - 新型Ti3+复合异质结构纳米材料的制备方法 - Google Patents
新型Ti3+复合异质结构纳米材料的制备方法 Download PDFInfo
- Publication number
- CN110124666A CN110124666A CN201910451538.7A CN201910451538A CN110124666A CN 110124666 A CN110124666 A CN 110124666A CN 201910451538 A CN201910451538 A CN 201910451538A CN 110124666 A CN110124666 A CN 110124666A
- Authority
- CN
- China
- Prior art keywords
- liquid
- junction structure
- nano material
- novel
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000010936 titanium Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000013049 sediment Substances 0.000 claims abstract description 9
- 150000003608 titanium Chemical class 0.000 claims abstract description 9
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 7
- 235000019441 ethanol Nutrition 0.000 claims description 18
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 11
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 8
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 229910019032 PtCl2 Inorganic materials 0.000 claims description 6
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 6
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 41
- 239000000463 material Substances 0.000 abstract description 30
- 238000001035 drying Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000000845 anti-microbial effect Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract 1
- 238000004435 EPR spectroscopy Methods 0.000 description 12
- 150000001298 alcohols Chemical class 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000002045 lasting effect Effects 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 2
- 229910003081 TiO2−x Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种新型Ti3+复合异质结构纳米材料的制备方法,将NaOH加入乙醇溶液中搅拌形成A液;将金属化合物在乙醇溶液中分散形成B液,然后加入钛盐形成C液;将A液滴入C液中,搅拌混匀得到混合溶液;置于反应釜中在160‑240℃下恒温反应至少3 h得到沉淀物;洗涤、干燥后得到Ti3+复合异质结构纳米材料。在材料制备过程中形成的Ti3+和氧空位以及金属单质,使TiO2的太阳能光吸收范围扩宽及抑制电子‑空穴的复合,进而提高材料的光催化性能、抗菌性能和降解性能。本发明采用溶剂热,通过控制反应条件可制备~10 nm的纳米金属单质修饰的Ti3+自掺杂异质结构复合材料,整个制备过程简单,具有实际应用前景。
Description
技术领域
本发明属于能源环境和光催化材料领域,具体涉及一种新型Ti3+复合异质结构纳米材料的制备方法。
背景技术
二氧化钛(TiO2)由于其广泛的应用范围和在基础水平上对表面性质的深入研究,在表面科学领域得到了广泛的研究。这些研究在一定程度上是因为发现TiO2是一种光催化剂,对水的分解和有机物的降解具有较高的效率,并且其化学性质非常稳定、价格低廉,在光催化去除环境中有害微生物和有机物。TiO2的光催化活性往往取决于表面缺陷中心的性质和密度。而 Ti3+被认为是许多吸附剂的重要反应剂,因此许多表面反应都受到这些点缺陷的影响。此外,在实际应用中,纯TiO2并不是一个很好的候选材料,因为它只有在紫外光(UV)照射下才具有活性,且纯的TiO2由于禁带宽度较宽(以锐钛矿为例~3.2 ev)仅能被太阳光中所占比例较少的紫外光(~4%)激发,然而,含有Ti3+的还原TiO2(TiO2−x)已被证明具有可见光吸收。
一般来说,Ti3+自掺杂TiO2光催化活性的增强主要是由于以下原因,其一,TiO2-x中Ti3+的存在增加了其光吸收区域,认为高浓度Ti3+掺杂导致TiO2的带隙变窄,TiO2的光吸收光谱范围通过自掺杂扩展到可见区域。其二,TiO2由Ti3+和氧空位引起的光载流子的高效分离和高导电性也是其增强光催化活性的重要原因。相关实验也证明了还原TiO2在可见光下的活性有所提高,说明引入Ti3+制备可见光响应型TiO2是可行的。因此,全面了解Ti3+生成制备的方法和技术是非常重要的。
为了使新型Ti3+复合异质结构纳米材料能够大规模的生产和实际应用,需要解决上述问题。
发明内容
本发明要解决的技术问题是针对纯TiO2宽禁带宽度导致的低吸收范围和电子-空穴易复合导致的催化效率等两大突出缺点,本发明提供一种新型Ti3+复合异质结构纳米材料的制备方法,利用简便的方法改善TiO2这一性质。一是通过Ti3+自掺杂拓宽改性TiO2的光吸收范围,得到具良好可见光响应的复合材料,二是通过合成中得到的金属单质抑制电子-空穴的复合。
复合材料制备后发现不仅含有Ti3+,而且还含有金属单质的纳米复合材料。进行材料测试的时候发现合成的纳米复合材料具有很强的协同效应,这是由于金属纳米粒子对二氧化钛进行修饰,可以改变体系中的电子分布,显著影响二氧化钛表面的光化学性质,进而提高其光催化活性,此外,Ti3+的存在增加了其光吸收区域,由Ti3+和氧空位引起的光载流子的高效分离和高导电性也是其增强光催化活性的重要原因。两者相互作用能有效提高所制备材料的杀菌性能,基于此提出了一种新型Ti3+复合异质结构纳米材料的制备方法。
为解决上述技术问题,本发明采用如下的技术方案:
一种新型Ti3+复合异质结构纳米材料的制备方法,包括以下步骤:
(1)将NaOH加入乙醇溶液中搅拌形成A液;
(2)将金属化合物在乙醇溶液中分散形成B液,然后加入钛盐形成C液;
(3)将A液滴入C液中,搅拌混匀得到混合溶液;
(4)将步骤(3)的混合液倒入反应釜中在温度160-240℃下恒温反应至少3 h,得到沉淀物;
(5)将步骤(4)的沉淀物用乙醇和水洗涤,干燥后得到Ti3+复合异质结构纳米材料。
进一步,所述金属化合物为PdCl2、PtCl2、NiCl2、CuCl2、RhCl3或RuCl3。
进一步,所述混合溶液中金属化合物的摩尔浓度为0.001 M。
进一步,所述钛盐为TiCl4,混合溶液中钛盐的摩尔浓度为0.1-0.5 M,优选0.1 M。
进一步,所述混合溶液中NaOH的摩尔浓度为0.4-0.6 M,优选0.4M。
进一步,所述步骤(4)中反应时间为3-10 h。
本发明给出具体反应体系中钛盐的摩尔浓度范围和金属离子(如:PdCl2、PtCl2、NiCl2、CuCl2、RhCl3、RuCl3等)浓度范围,在范围中都可以得到异质复合材料,在进一步给出的优化范围中,可以得到Ti3+信号较强的异质复合材料。本发明中的异质复合材料在可见光下具有响应,关键因素在于所使用的金属离子(如:PdCl2、PtCl2、NiCl2、CuCl2、RhCl3、RuCl3等)在钛盐中的反应。本发明反应所需的温度条件,低于160℃不能很好的晶化;160℃以上时,可以得到锐钛矿相二氧化钛,温度越高,所得材料晶化越好,高于240℃后,反应危险性增加。所需反应时间,反应时间>3h就可以得到异质复合材料,过多延长时间不有利于反应得完全进行。
本发明设计原理如下:
利用金属离子(如:PdCl2、PtCl2、NiCl2、CuCl2、RhCl3、RuCl3等)与钛在醇溶剂环境中反应,再将含NaOH的醇溶剂滴入含金属离子(如:PdCl2、PtCl2、NiCl2、CuCl2、RhCl3、RuCl3等)与钛的醇溶剂中,通过水热的方法,制备一系列新型Ti3+复合异质结构纳米材料。
本发明具有如下的优点以及技术效果:
1. 本发明利用纳米金属颗粒(如:Pd、Pt、Ni、Cu、Rh、Ru等)抑制电子-空穴的复合,提高材料光催化效率。
2. 本发明引入Ti3+掺杂降低TiO2禁带宽度,拓宽改性TiO2的光吸收范围,得到具良好可见光响应的复合材料。
3. 本发明通过一步溶剂的方法,制备一系列纳米金属颗粒修饰的Ti3+自掺杂新型复合异质结构纳米材料,操作简单,易于控制。
4. 本发明方法制得的复合材料,经生物安全检测无毒、稳定性高、抗菌性能好,适合用于涂料、食品保鲜膜等一系列工艺中,前景广阔。
5. 本发明提供的新型Ti3+复合异质结构纳米材料的制备方法,即一步合成,不需要高温、离子体处理、激光或中子束辐照等,操作简便,安全性高。
附图说明
图1为本发明实施例1制备的Pd/Ti3+-TiO2的XRD照片;
图2为本发明实施例1制备的Pd/Ti3+-TiO2的UV-Vis照片;
图3为本发明实施例1制备的Pd/Ti3+-TiO2的TEM图谱;
图4为本发明实施例1制备的Pd/Ti3+-TiO2的XPS谱图;
图5为本发明实施例1制备的Pd/Ti3+-TiO2的EPR图;
图6为本发明实施例2制备的Pt/Ti3+-TiO2的EPR图;
图7为本发明实施例3制备的Ni/Ti3+-TiO2的EPR图;
图8为本发明实施例4制备的Cu/Ti3+-TiO2的EPR图;
图9为本发明实施例5制备的Rh/Ti3+-TiO2的EPR图;
图10为本发明实施例6制备的Ru/Ti3+-TiO2的EPR图。
具体实施方式
实施例1
本实施例的新型Ti3+复合异质结构纳米材料的制备方法如下:
(1)在室温下,将24 mmol NaOH加入到30 mL无水乙醇中在密闭条件下持续搅拌形成混合溶液A;
(2)将0.06 mmol的PdCl2溶于30 mL无水乙醇中,在超声波清洗机中超声20 min,以保证氯化钯均匀分散,形成B液,然后待A液中NaOH快溶解完时,将6 mmol(0.66 mL)TiCl4加入B液形成混合溶液C,将混合液C继续搅拌2~3 min;
(3)将A液缓慢滴入混合液C,搅拌20 min后转移到聚四氟乙烯的不锈钢反应釜中,置于恒温干燥箱中180℃ 4 h。待反应结束且温度降低至室温时,把得到的沉淀物用去离子水和无水乙醇洗涤,去除未反应的杂质。将洗涤后的产物放入烘箱中60℃烘干过夜,研磨成粉末;样品记为A。
采用德国Bruker公司D8 Advance型X射线衍射仪对得到的样品进行XRD分析。如图1所示为样品的XRD谱图,XRD谱图显示样品为锐钛矿相二氧化钛和立方相氯化银。采用日本日立公司U-3900H紫外可见光固体漫反射仪器对样品光吸收进行分析,如图2所示制备的材料有较好的可见光吸收效果。
采用日本电子JSM-6490LV型扫描电子显微镜和日本电子2100型透射电子显微镜观察得到样品的形貌结构,如图3所示为样品的TEM照片,结果可见,所得Pd/Ti3+-TiO2的尺寸大约为10 nm,相对均匀。
采用美国Thermo公司的ESCALAB 250型X-射线光电子能谱仪进行XPS分析,如图4所示图中Ti2p 谱拟合为459.8 eV、458.6 eV和465.0 eV的三个峰,分别对应Ti2p 3/2- Ti4+、Ti2p 3/2- Ti3+和Ti2p 1/2。采用日本JEOL公司的JES-FA200型的电子自旋共振谱仪测试材料三价钛信号的强弱,如图5所示。
实施例2
本实施例的新型Ti3+复合异质结构纳米材料的制备方法如下:
(1)室温,将24 mmol NaOH加入到30 mL无水乙醇中在密闭条件下持续搅拌形成混合溶液A;
(2)将0.06 mmol的PtCl2溶于30 mL无水乙醇中,在超声波清洗机中超声20 min,以保证氯化钯均匀分散,形成B液,然后待A液中NaOH快融解完时,将6 mmol(0.66 mL)TiCl4加入B液形成混合溶液C,将混合液C继续搅拌2~3 min;
(3)将A液缓慢滴入混合液C,搅拌20 min后转移到聚四氟乙烯的不锈钢反应釜中,置于恒温干燥箱中160℃ 8 h。待反应结束且温度降低至室温时,把得到的沉淀物用去离子水和无水乙醇洗涤,去除未反应的杂质。将洗涤后的产物放入烘箱中60℃烘干过夜,研磨成粉末;样品记为B。
采用实施例1的设备对样品进行检测,样品B的EPR图如图6,所得Pt/Ti3+- TiO2材料含有Ti3+信号。
实施例3
本实施例的新型Ti3+复合异质结构纳米材料的制备方法如下:
(1)室温,将24 mmol NaOH加入到30 mL无水乙醇中在密闭条件下持续搅拌形成混合溶液A;
(2)将0.06 mmol的NiCl2溶于30 mL无水乙醇中,在超声波清洗机中超声20 min,以保证氯化钯均匀分散,形成B液,然后待A液中NaOH快融解完时,将6 mmol(0.66 mL)TiCl4加入B液形成混合溶液C,将混合液C继续搅拌2~3 min;
(3)将A液缓慢滴入混合液C,搅拌20 min后转移到聚四氟乙烯的不锈钢反应釜中,置于恒温干燥箱中180℃ 10 h。待反应结束且温度降低至室温时,把得到的沉淀物用去离子水和无水乙醇洗涤,去除未反应的杂质。将洗涤后的产物放入烘箱中60℃烘干过夜,研磨成粉末;样品记为C。
采用实施例1的设备对样品进行检测,样品C的EPR图如图7,所得Ni/Ti3+- TiO2材料含有Ti3+信号。
实施例4
本实施例的新型Ti3+复合异质结构纳米材料的制备方法如下:
(1)室温,将24 mmol NaOH加入到30 mL无水乙醇中在密闭条件下持续搅拌形成混合溶液A;
(2)将0.06 mmol的CuCl2溶于30 mL无水乙醇中,在超声波清洗机中超声20 min,以保证氯化钯均匀分散,形成B液,然后待A液中NaOH快融解完时,将6 mmol(0.66 mL)TiCl4加入B液形成混合溶液C,将混合液C继续搅拌2~3 min;
(3)将A液缓慢滴入混合液C,搅拌20 min后转移到聚四氟乙烯的不锈钢反应釜中,置于恒温干燥箱中200℃ 6 h。待反应结束且温度降低至室温时,把得到的沉淀物用去离子水和无水乙醇洗涤,去除未反应的杂质。将洗涤后的产物放入烘箱中60℃烘干过夜,研磨成粉末;样品记为D。
采用实施例1的设备对样品进行检测,样品D的EPR图如图8,所得Cu/Ti3+- TiO2材料含有Ti3+信号。
实施例5
本实施例的新型Ti3+复合异质结构纳米材料的制备方法如下:
(1)室温,将24 mmol NaOH加入到30 mL无水乙醇中在密闭条件下持续搅拌形成混合溶液A;
(2)将0.06 mmol的RhCl2溶于30 mL无水乙醇中,在超声波清洗机中超声20 min,以保证氯化钯均匀分散,形成B液,然后待A液中NaOH快融解完时,将6 mmol(0.66 mL)TiCl4加入B液形成混合溶液C,将混合液C继续搅拌2~3 min;
(3)将A液缓慢滴入混合液C,搅拌20 min后转移到聚四氟乙烯的不锈钢反应釜中,置于恒温干燥箱中220℃ 4 h。待反应结束且温度降低至室温时,把得到的沉淀物用去离子水和无水乙醇洗涤,去除未反应的杂质。将洗涤后的产物放入烘箱中60℃烘干过夜,研磨成粉末;样品记为E。
采用实施例1的设备对样品进行检测,样品E的EPR图如图9,所得Rh/Ti3+- TiO2材料含有Ti3+信号。
实施例6
本实施例的新型Ti3+复合异质结构纳米材料的制备方法如下:
(1)室温,将24 mmol NaOH加入到30 mL无水乙醇中在密闭条件下持续搅拌形成混合溶液A;
(2)将0.06 mmol的RuCl2溶于30 mL无水乙醇中,在超声波清洗机中超声20 min,以保证氯化钯均匀分散,形成B液,然后待A液中NaOH快融解完时,将6 mmol(0.66 mL)TiCl4加入B液形成混合溶液C,将混合液C继续搅拌2~3 min;
(3)将A液缓慢滴入混合液C,搅拌20 min后转移到聚四氟乙烯的不锈钢反应釜中,置于恒温干燥箱中240℃ 3 h。待反应结束且温度降低至室温时,把得到的沉淀物用去离子水和无水乙醇洗涤,去除未反应的杂质。将洗涤后的产物放入烘箱中60℃烘干过夜,研磨成粉末;样品记为F。
采用实施例1的设备对样品进行检测,样品F的EPR图如图10,所得Ru/Ti3+- TiO2材料含有Ti3+信号。
除乙醇外其他醇在本发明中作用相同,它们的性质相近,所制得的材料没有太大差别,故在没有给出实施例的前提下,能够预想得到相同的技术效果。
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (6)
1.一种新型Ti3+复合异质结构纳米材料的制备方法,其特征在于:包括以下步骤:
(1)将NaOH加入乙醇溶液中搅拌形成A液;
(2)将金属化合物在乙醇溶液中分散形成B液,然后加入钛盐形成C液;
(3)将A液滴入C液中,搅拌混匀得到混合溶液;
(4)将步骤(3)的混合液倒入反应釜中在温度160-240℃下恒温反应至少3 h,得到沉淀物;
(5)将步骤(4)的沉淀物用乙醇和水洗涤,干燥后得到Ti3+复合异质结构纳米材料。
2.根据权利要求1所述的新型Ti3+复合异质结构纳米材料的制备方法,其特征在于:所述金属化合物为PdCl2、PtCl2、NiCl2、CuCl2、RhCl3或RuCl3。
3.根据权利要求1所述的新型Ti3+复合异质结构纳米材料的制备方法,其特征在于:所述混合溶液中金属化合物的摩尔浓度为0.001 M。
4.根据权利要求1所述的新型Ti3+复合异质结构纳米材料的制备方法,其特征在于:所述钛盐为TiCl4,混合溶液中钛盐的摩尔浓度为0.1-0.5 M。
5.根据权利要求1所述的新型Ti3+复合异质结构纳米材料的制备方法,其特征在于:所述混合溶液中NaOH的摩尔浓度为0.4-0.6 M。
6.根据权利要求1所述的新型Ti3+复合异质结构纳米材料的制备方法,其特征在于:所述步骤(4)中反应时间为3-10 h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910451538.7A CN110124666B (zh) | 2019-05-28 | 2019-05-28 | 新型Ti3+复合异质结构纳米材料的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910451538.7A CN110124666B (zh) | 2019-05-28 | 2019-05-28 | 新型Ti3+复合异质结构纳米材料的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110124666A true CN110124666A (zh) | 2019-08-16 |
CN110124666B CN110124666B (zh) | 2022-09-16 |
Family
ID=67582305
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910451538.7A Active CN110124666B (zh) | 2019-05-28 | 2019-05-28 | 新型Ti3+复合异质结构纳米材料的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110124666B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111068671A (zh) * | 2019-12-19 | 2020-04-28 | 西安近代化学研究所 | 一种高选择性氨基酸脱羧催化剂及其制备方法 |
CN111072493A (zh) * | 2019-12-19 | 2020-04-28 | 西安近代化学研究所 | 一种一步法制备1,5-戊二胺的方法 |
CN113680344A (zh) * | 2021-08-03 | 2021-11-23 | 江苏大学 | 一种富含氧空位/Ru掺杂的TiO2纳米晶体的制备方法及用途 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2687288A1 (en) * | 2012-07-19 | 2014-01-22 | Sociedad española de carburos metalicos, S.A. | Method for predicting the efficiency of a TIO2 photocatalyst |
CN105921149A (zh) * | 2016-05-12 | 2016-09-07 | 岭南师范学院 | 一种溶剂热制备铜修饰二氧化钛纳米棒的方法 |
CN106732590A (zh) * | 2016-11-24 | 2017-05-31 | 郑州轻工业学院 | 一种铜/氧化钛光催化纳米材料的制备方法 |
CN107737593A (zh) * | 2017-11-10 | 2018-02-27 | 河北工业大学 | 一种TiO2纳米管负载的双金属催化剂的制备方法 |
-
2019
- 2019-05-28 CN CN201910451538.7A patent/CN110124666B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2687288A1 (en) * | 2012-07-19 | 2014-01-22 | Sociedad española de carburos metalicos, S.A. | Method for predicting the efficiency of a TIO2 photocatalyst |
CN105921149A (zh) * | 2016-05-12 | 2016-09-07 | 岭南师范学院 | 一种溶剂热制备铜修饰二氧化钛纳米棒的方法 |
CN106732590A (zh) * | 2016-11-24 | 2017-05-31 | 郑州轻工业学院 | 一种铜/氧化钛光催化纳米材料的制备方法 |
CN107737593A (zh) * | 2017-11-10 | 2018-02-27 | 河北工业大学 | 一种TiO2纳米管负载的双金属催化剂的制备方法 |
Non-Patent Citations (3)
Title |
---|
HUANLI WANG,LISHA ZHANG ET AL.: ""Semiconductor heterojunction photocatalysts:design,construction,and photocatalytic performances"", 《CHEMICAL SOCIETY REVIEWS》 * |
PING WANG,SHUNQIU XU,FENG CHEN,HUOGEN YU: "Ni nanoparticles as electron-transfer mediators and NiSx as interfacial active sites for coordinative enhancement of H2-evolution performance of TiO2", 《CHINESE JOURNAL OF CATALYSIS》 * |
荆洁颖 著: "《高分散纳米催化剂制备及光催化应用》", 30 September 2017, 冶金工业出版社 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111068671A (zh) * | 2019-12-19 | 2020-04-28 | 西安近代化学研究所 | 一种高选择性氨基酸脱羧催化剂及其制备方法 |
CN111072493A (zh) * | 2019-12-19 | 2020-04-28 | 西安近代化学研究所 | 一种一步法制备1,5-戊二胺的方法 |
CN111072493B (zh) * | 2019-12-19 | 2023-07-14 | 西安近代化学研究所 | 一种一步法制备1,5-戊二胺的方法 |
CN113680344A (zh) * | 2021-08-03 | 2021-11-23 | 江苏大学 | 一种富含氧空位/Ru掺杂的TiO2纳米晶体的制备方法及用途 |
Also Published As
Publication number | Publication date |
---|---|
CN110124666B (zh) | 2022-09-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zeng et al. | Nanoscale lightning rod effect in 3D carbon nitride nanoneedle: Enhanced charge collection and separation for efficient photocatalysis | |
CN101347725B (zh) | 碳纳米管/二氧化钛纳米复合光催化剂及其用途 | |
Chen et al. | Surface interaction between cubic phase NaNbO3 nanoflowers and Ru nanoparticles for enhancing visible-light driven photosensitized photocatalysis | |
CN110124666A (zh) | 新型Ti3+复合异质结构纳米材料的制备方法 | |
Liu et al. | One-step synthesis of metallic Bi deposited Bi2WO6 nanoclusters for enhanced photocatalytic performance: An experimental and DFT study | |
Wei et al. | Influence of surfactant on the morphology and photocatalytic activity of anatase TiO2 by solvothermal synthesis | |
Girginov et al. | Silver doped TiO2 photocatalyst for methyl orange degradation | |
Baral et al. | A review of recent progress on nano MnO 2: synthesis, surface modification and applications | |
CN107159192B (zh) | 一种贵金属/TiO2混晶纳米棒组装多级结构的制备方法 | |
Peng et al. | Fabrication of fibrous BiVO4/Bi2S3/MoS2 heterojunction and synergetic enhancement of photocatalytic activity towards pollutant degradation | |
Bao et al. | CuWO4-x nanoparticles incorporated brookite TiO2 porous nanospheres: Preparation and dramatic photocatalytic activity for light driven H2 generation | |
Hou et al. | Effect of platinum dispersion on photocatalytic performance of Pt-TiO 2 | |
Wang et al. | One-step synthesis of nonstoichiometric TiO2 with designed (101) facets for enhanced photocatalytic H2 evolution | |
Liu et al. | F-regulate the preparation of polyhedral BiVO4 enclosed by High-Index facet and enhance its photocatalytic activity | |
Nalajala et al. | Aqueous methanol to formaldehyde and hydrogen on Pd/TiO2 by photocatalysis in direct sunlight: structure dependent activity of nano-Pd and atomic Pt-coated counterparts | |
CN100434165C (zh) | 高活性纳米晶BiVO4可见光催化剂的超声化学的制备方法 | |
Kim et al. | New fan blade-like core-shell Sb2TixSy photocatalytic nanorod for hydrogen production from methanol/water photolysis | |
Fang et al. | In-situ monitoring of dynamic behavior of catalyst materials and reaction intermediates in semiconductor catalytic processes | |
CN105834448A (zh) | 一步法制备Ag@TiO2纳米复合材料 | |
Wang et al. | Facile synthesize of CdS QDs decorated Bi2MoO6/Bi2Mo3O12 heterojunction photocatalysts and enhanced performance of visible light removal of organic pollutants | |
Li et al. | In situ construction of oxygen deficient MoO3-x nanosheets/porous graphitic carbon nitride for enhanced photothermal-photocatalytic hydrogen evolution | |
Zhou et al. | Investigation of photocatalytic performance of CuS/Bi2WO6 and degradation pathway of RhB in water | |
Su et al. | Effect of Cr and La co-doping on the photocatalytic hydrogen production performance of Sr1-xLaxTi1-xCrxO3 nanofibers | |
Elmaci | Microwave assisted green synthesis of Ag/AgO nanocatalyst as an efficient OER catalyst in neutral media | |
CN106964352B (zh) | 新型光催化材料TiO2@Fe2O3、SrTiO3@Fe2O3的制备及应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |