CN107413338A - 一种金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法 - Google Patents
一种金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法 Download PDFInfo
- Publication number
- CN107413338A CN107413338A CN201710295228.1A CN201710295228A CN107413338A CN 107413338 A CN107413338 A CN 107413338A CN 201710295228 A CN201710295228 A CN 201710295228A CN 107413338 A CN107413338 A CN 107413338A
- Authority
- CN
- China
- Prior art keywords
- nano
- tube array
- metal rhodium
- rhodium
- tio
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002071 nanotube Substances 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 71
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 60
- 239000010948 rhodium Substances 0.000 title claims abstract description 60
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 48
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 238000000137 annealing Methods 0.000 claims abstract description 14
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000012798 spherical particle Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 229960005196 titanium dioxide Drugs 0.000 description 7
- 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 6
- 235000013339 cereals Nutrition 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000758 substrate Substances 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
- B01J23/46—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
- B01J37/0226—Oxidation of the substrate, e.g. anodisation
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Toxicology (AREA)
- Thermal Sciences (AREA)
- Electrochemistry (AREA)
- Plasma & Fusion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法,包括如下步骤:预处理、阳极氧化、负载金属铑颗粒、退火。本发明原料简单易得,以硝酸铑和乙二醇为原料,工艺过程简单,获得的铑纳米颗粒在纳米管表面均匀分布,且呈球状粒径大小均匀,由于金属离子共振效应的作用,铑纳米颗粒的负载可以有效地提高二氧化钛纳米管材料的光催化活性。
Description
技术领域
本发明涉及一种金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法。
背景技术
二氧化钛纳米管半导体材料因为其的光催化性一直备受关注,但是在实际应用中存在不足之处,主要有两点:一、TiO2的禁带宽度为3.2eV,相对较宽,基本上只能被波长小于386nm的光子激发,从而光谱响应的范围较窄,波长小于386nm的光只占太阳能的 3%-4%,这样就限制了对太阳光的利用率;二、量子效率低,因为在TiO2中光生电子迁移速率较慢,而空穴的氧化速率很快,常常在导带中积累,光生电子的积累增加了与光生空穴复合的几率,这将降低TiO2半导体材料的光催化效率。为了解决这些问题研究者们利用金属表面等离子体效应对TiO2纳米管阵列材料进行改性,并初见成效。不过金属使用范围主要是贵金属金、铂、银等纳米颗粒。因为金属铑纳米颗粒也是一种催化剂,那么将金属铑颗粒负载于二氧化钛纳米管表面两者结合,此做法为提高TiO2纳米管阵列材料的光催化活性提供了新思路。
利用金属表面等离子体效应改性二氧化钛纳米管材料,提高其光催化活性的工作主要是采用的金属银、铂、金纳米颗粒,对于金属铑纳米颗粒改性TiO2纳米管阵列光催化材料的制备方法的研究相对较少。以往都是采用沉积-沉淀法进行金属纳米颗粒的负载,此方法不能完全适用于金属铑纳米颗粒的负载于TiO2纳米管阵列材料。因此,开发一种可以将金属铑纳米颗粒均匀地负载于TiO2纳米管阵列材料的方法具有重要的实用价值。
发明内容
基于以上现有技术的不足,本发明所解决的技术问题在于提供一种可以将金属铑纳米颗粒均匀地负载于TiO2纳米管阵列材料表面,并且制备的金属铑纳米颗粒改性的TiO2纳米管阵列光催化材料表面形貌较好,光催化活性较高的的方法。
为了解决上述技术问题,本发明提供一种金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法,包括如下步骤:
预处理、阳极氧化、负载金属铑颗粒。
所述预处理包括如下步骤:
步骤一、将钛片进行机械抛光,再进行超声清洗。
所述阳极氧化包括如下步骤:
步骤二、向甘油与水体积比为2:1的混合溶液中添加0.5wt%的NH4F,得到电解液;
步骤三、室温下,使用预处理后的钛片作为阳极,在步骤二制得的电解液中阳极氧化4h,氧化电压20v,退火处理,得到锐钛矿相的TiO2纳米管阵列材料。
作为上述技术方案的优选实施方式,本发明实施例提供的金属铑纳米颗粒改性TiO2纳米管阵列光催化材料的制备方法进一步包括下列技术特征的部分或全部:
作为上述技术方案的改进,在本发明的一个实施例中,所述步骤三中,退火处理为,450℃温度下退火2h,然后冷却至室温。
所述负载金属铑颗粒包括如下步骤:
步骤四、将步骤三所得TiO2纳米管阵列材料放入硝酸铑溶液中恒温水浴浸泡;
步骤五、将步骤四所得样品放入乙二醇中浸泡反应;
步骤六、取负载金属铑颗粒后的样品,退火处理。
作为上述技术方案的优选实施方式,本发明实施例提供的金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法进一步包括下列技术特征的部分或全部:
作为上述技术方案的改进,在本发明的一个实施例中,所述步骤四中,硝酸铑溶液为0.002~0.005mol/L,浸泡时间8h,恒温水浴温度70℃。
作为上述技术方案的改进,在本发明的一个实施例中,步骤五的反应时间为12~24h。
作为上述技术方案的改进,在本发明的一个实施例中,所述步骤六中,退火处理为,将样品放入马沸炉中氮气气氛下450-600℃下退火5h,然后冷却至室温,得到金属铑纳米颗粒负载的TiO2纳米管阵列材料。
本发明基本原理是利用阳极氧化法将Ti基片经过电化学氧化和化学腐蚀两个过程得到TiO2纳米管阵列材料,通过严格精确控制阳极氧化氧化电压、电解液组成、氧化时间等条件快速制备表面形貌排列整齐有序的二氧化钛纳米管阵列材料。将得到的二氧化钛纳米管阵列材料退火得到锐钛矿相的TiO2纳米管阵列材料。为了将金属铑纳米颗粒负载于纳米管的表面,采用的原理是:首先,将二氧化钛纳米管材料放入硝酸铑溶液中进行浸泡,因为硝酸铑具有氧化性,同时乙二醇具有还原性,将浸泡过的样品放入乙二醇溶剂中充分反应,再退火,最后得到金属铑纳米颗粒改性TiO2纳米管阵列光催化材料。
本发明利用简单易得的原料,且工艺简单、反应时间短、得到的材料光催化性能较好。金属铑纳米颗粒大小均匀,并且均匀地分布在纳米管的内外壁以及纳米管的顶端。
本发明的有益效果在于:本发明以阳极氧化法制备的二氧化钛纳米管阵列材料为基础,硝酸铑溶液作为铑源,乙二醇作为还原剂,经过液相反应退火后,就可以得到负载有金属铑纳米颗粒的 TiO2纳米管阵列光催化材料;本发明制备的金属铑纳米颗粒形貌为球状,且颗粒大小均匀,分布均匀。通过测试催化降解亚甲基蓝溶液表征其光催化性能较未改性的二氧化钛纳米管材料有一定的提高。同时,本发明基本填补了利用金属铑纳米颗粒改性二氧化钛纳米管材料的空白。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,而可依照说明书的内容予以实施,并且为了让本发明的上述和其他目的、特征和优点能够更明显易懂,以下结合优选实施例,详细说明如下。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例的附图作简单地介绍。
图1为本发明实施例1所制备的金属铑纳米颗粒改性TiO2纳米管阵列光催化材料的扫描电镜图(SEM),其中图(a)和图(b)分别为未负载和负载有金属铑纳米颗粒的TiO2纳米管阵列的扫描电镜图;
图2为实施例3所制备的金属铑纳米颗粒改性TiO2纳米管阵列光催化材料的扫描电镜图(SEM);
图3为实施例3所制备的金属铑纳米颗粒改性TiO2纳米管阵列光催化材料的XRD图;
图4为实施例4所制备的金属铑纳米颗粒改性TiO2纳米管阵列光催化材料的扫描电镜图(SEM);
图5为实施例4所制备的金属铑纳米颗粒改性TiO2纳米管阵列光催化材料的催化降解图。
具体实施方式
下面详细说明本发明的具体实施方式,其作为本说明书的一部分,通过实施例来说明本发明的原理,本发明的其他方面、特征及其优点通过该详细说明将会变得一目了然。
实施例1
制备金属铑纳米颗粒改性TiO2纳米管阵列光催化材料,步骤如下:
步骤一、将钛片进行机械抛光,再进行超声清洗。
步骤二、将1.76g氟化铵溶质溶于由100mL和200mL组成的混合溶液中,充分搅拌2h,得到阳极氧化反应所用的电解液。
步骤三、然后将预处理后的钛片作为阳极材料,铂片作为阴极材料,外加电压20v,氧化时间4h得到无定型TiO2纳米管阵列材料,再经过退火处理得到锐钛矿相的TiO2纳米管阵列材料。
步骤四、将TiO2纳米管阵列材料放入浓度0.002mol/L的硝酸铑溶液中,于70℃的恒温条件下浸泡8h,浸泡结束后并用去离子水洗涤3次
步骤五、将步骤四所得样品置于乙二醇溶剂中反应12h。
步骤六、将步骤五所得样品置于450℃的氮气氛围的炉中退火 5h,得到金属铑纳米颗粒改性TiO2纳米管阵列光催化材料。
本实施例所得材料的扫描电子显微镜(SEM)对其形貌进行了表征。图1为本实施例所制备的TiO2纳米管阵列及负载有金属铑纳米颗粒的TiO2纳米管阵列的扫描电镜图,图(a)和(b)分别为未负载铑纳米颗粒和负载有铑纳米颗粒的TiO2纳米管阵列的扫描电子显微镜的表面形貌图。从图(a)可知得到纳米管的管外径为80~ 100nm,列形貌较为整齐有序。此外,从图(b)可知有金属铑纳米颗粒生成并附着于纳米管的管壁内外,只是颗粒尺寸很小,大小在 5~8nm之间。
实施例2
制备金属铑纳米颗粒改性TiO2纳米管阵列光催化材料,步骤如下:
步骤一、将钛片进行机械抛光,再进行超声清洗。
步骤二、将1.76g氟化铵溶质溶于由100mL和200mL组成的混合溶液中,充分搅拌4h,得到阳极氧化反应所用的电解液。
步骤三、然后将预处理后的钛片作为阳极材料,铂片作为阴极材料,外加电压20v,氧化时间4h得到无定型TiO2纳米管阵列材料,再经过退火处理得到锐钛矿相的TiO2纳米管阵列材料。
步骤四、将TiO2纳米管阵列材料放入浓度0.003mol/L的硝酸铑溶液中,于70℃的恒温条件下浸泡8h,浸泡结束后并用去离子水洗涤3次
步骤五、将步骤四所得样品置于乙二醇溶剂中反应12h。
步骤六、将步骤五所得样品置于500℃的氮气氛围的炉中退火 5h,得到金属铑纳米颗粒改性TiO2纳米管阵列光催化材料。
实施例3
制备金属铑纳米颗粒改性TiO2纳米管阵列光催化材料,步骤如下:
步骤一、将钛片进行机械抛光,再进行超声清洗。
步骤二、将1.76g氟化铵溶质溶于由100mL和200mL组成的混合溶液中,充分搅拌2h,得到阳极氧化反应所用的电解液。
步骤三、然后将预处理后的钛片作为阳极材料,铂片作为阴极材料,外加电压20v,氧化时间4h得到无定型TiO2纳米管阵列材料,再经过退火处理得到锐钛矿相的TiO2纳米管阵列材料。
步骤四、将TiO2纳米管阵列材料放入浓度0.004mol/L的硝酸铑溶液中,于70℃的恒温条件下浸泡8h,浸泡结束后并用去离子水洗涤3次
步骤五、将步骤四所得样品置于乙二醇溶剂中反应18h。
步骤六、将步骤五所得样品置于550℃的氮气氛围的炉中退火 5h,得到金属铑纳米颗粒改性TiO2纳米管阵列光催化材料。
图2为本实施例所制备的金属铑纳米颗粒改性TiO2纳米管阵列光催化材料的扫描电镜图(SEM),铑纳米颗粒大小较实施例1和2 中的对比其尺寸有所变大,且颗粒明显呈现为球状,粒径为15~ 20nm,均匀分布于纳米管的管内外壁和纳米管与纳米管的间隙之中。
图3为本实施例所得材料的XRD图,结果表明生成物相中除了有金属钛和二氧化钛的锐钛矿相,还有金属铑单质的物相。
实施例4
制备金属铑纳米颗粒改性TiO2纳米管阵列光催化材料,步骤如下:
步骤一、将钛片进行机械抛光,再进行超声清洗。
步骤二、将1.76g氟化铵溶质溶于由100mL和200mL组成的混合溶液中,充分搅拌2h,得到阳极氧化反应所用的电解液。
步骤三、然后将预处理后的钛片作为阳极材料,铂片作为阴极材料,外加电压20v,氧化时间4h得到无定型TiO2纳米管阵列材料,再经过退火处理得到锐钛矿相的TiO2纳米管阵列材料。
步骤四、将TiO2纳米管阵列材料放入浓度0.005mol/L的硝酸铑溶液中,于70℃的恒温条件下浸泡8h,浸泡结束后并用去离子水洗涤3次
步骤五、将步骤四所得样品置于乙二醇溶剂中反应24h。
步骤六、将步骤五所得样品置于600℃的氮气氛围的炉中退火 5h,得到金属铑纳米颗粒改性TiO2纳米管阵列光催化材料。
图4为本实施例制备的金属铑纳米颗粒改性TiO2纳米管阵列光催化材料的扫描电镜图(SEM)。得到的金属铑纳米颗粒的大小与实施例3的对比其大小变化不大,但粒径大小依旧较为均匀,粒径为 15~25nm。将本实施例所得材料在紫外光光强0.7mW/cm2照射,室温条件下(约为25℃),以1.0×10-5M的亚甲基蓝溶液为目标降解溶液,测试其光催化活性。金属铑纳米颗粒改性的TiO2纳米管阵列光催化材料催化降解亚甲基蓝溶液的曲线见图5,图5为实施例4 所制备的金属铑纳米颗粒改性TiO2纳米管阵列光催化材料的催化降解图,其中在催化降解亚甲基蓝的过程中,反应物浓度与降解速率的符合准一级动力学方程C0和Ct分别为初始时和当光照时间为t时的亚甲基蓝水溶液的浓度,对亚甲基蓝溶液光照不同时间后的吸光度进行线性拟合可得催光催化表观反应速度常数k,用来判断样品的光催化活性,k值越大,则光催化性能越好。
以上所述是本发明的优选实施方式而已,当然不能以此来限定本发明之权利范围,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和变动,这些改进和变动也视为本发明的保护范围。
Claims (5)
1.一种金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法,其特征在于,包括如下步骤:
步骤一、将钛片进行机械抛光,再进行超声清洗;
步骤二、向甘油与水体积比为2:1的混合溶液中添加0.5wt%的NH4F,得到电解液;
步骤三、室温下,使用预处理后的钛片作为阳极,在步骤二制得的电解液中阳极氧化4h,氧化电压20v,退火处理,得到锐钛矿相的TiO2纳米管阵列材料;
步骤四、将步骤三所得TiO2纳米管阵列材料放入硝酸铑溶液中恒温水浴浸泡,浸泡结束后用去离子水洗涤3次;
步骤五、将步骤四所得样品放入乙二醇中浸泡反应;
步骤六、取负载金属铑颗粒后的样品,退火处理。
2.如权利要求1所述的金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法,其特征在于:所述步骤三中,退火处理为,450℃温度下退火2h,然后冷却至室温。
3.如权利要求1所述的金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法,其特征在于:所述步骤四中,硝酸铑溶液为0.002~0.005mol/L,浸泡时间8h,恒温水浴温度70℃。
4.如权利要求1所述的金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法,其特征在于:步骤五的反应时间为12~24h。
5.如权利要求1所述的金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法,其特征在于:所述步骤六中,退火处理为,将样品放入马沸炉中氮气气氛下450-600℃下退火5h,然后冷却至室温,得到金属铑纳米颗粒负载的TiO2纳米管阵列材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710295228.1A CN107413338A (zh) | 2017-04-28 | 2017-04-28 | 一种金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710295228.1A CN107413338A (zh) | 2017-04-28 | 2017-04-28 | 一种金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107413338A true CN107413338A (zh) | 2017-12-01 |
Family
ID=60424827
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710295228.1A Pending CN107413338A (zh) | 2017-04-28 | 2017-04-28 | 一种金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107413338A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021120359A1 (zh) * | 2019-12-19 | 2021-06-24 | 华中科技大学 | 单原子贵金属锚定缺陷型WO3/TiO2纳米管、其制备和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1927451A (zh) * | 2006-09-22 | 2007-03-14 | 中国海洋大学 | 一种纳米粉体的制备方法 |
CN101187043A (zh) * | 2007-09-17 | 2008-05-28 | 西北有色金属研究院 | 具有光催化性能的超长二氧化钛纳米管阵列的制备方法 |
CN103243336A (zh) * | 2013-05-15 | 2013-08-14 | 中南大学 | 一种纳米铂/二氧化钛纳米管阵列复合材料的制备方法 |
-
2017
- 2017-04-28 CN CN201710295228.1A patent/CN107413338A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1927451A (zh) * | 2006-09-22 | 2007-03-14 | 中国海洋大学 | 一种纳米粉体的制备方法 |
CN101187043A (zh) * | 2007-09-17 | 2008-05-28 | 西北有色金属研究院 | 具有光催化性能的超长二氧化钛纳米管阵列的制备方法 |
CN103243336A (zh) * | 2013-05-15 | 2013-08-14 | 中南大学 | 一种纳米铂/二氧化钛纳米管阵列复合材料的制备方法 |
Non-Patent Citations (3)
Title |
---|
刘光复: "《安徽节能减排博士科技论坛论文集》", 30 November 2007, 合肥工业大学出版社 * |
周正华: "《纳米材料开放使用及质量检测技术标准应用手册》", 30 April 2005, 银声音像出版社 * |
曹殿学: "《燃料电池系统》", 30 September 2009, 北京航空航天大学出版社 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021120359A1 (zh) * | 2019-12-19 | 2021-06-24 | 华中科技大学 | 单原子贵金属锚定缺陷型WO3/TiO2纳米管、其制备和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Andronic et al. | Black TiO2 synthesis by chemical reduction methods for photocatalysis applications | |
JP6876778B2 (ja) | 複合光触媒の製造方法、及び、複合光触媒 | |
WO2021120359A1 (zh) | 单原子贵金属锚定缺陷型WO3/TiO2纳米管、其制备和应用 | |
Momeni et al. | Fabrication, characterization and photoelectrochemical performance of chromium-sensitized titania nanotubes as efficient photoanodes for solar water splitting | |
Chen et al. | Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications | |
Siuleiman et al. | Photodegradation of Orange II by ZnO and TiO2 powders and nanowire ZnO and ZnO/TiO2 thin films | |
Yu et al. | Fabrication and characterization of visible-light-driven plasmonic photocatalyst Ag/AgCl/TiO2 nanotube arrays | |
Pareek et al. | Nanoniobia modification of CdS photoanode for an efficient and stable photoelectrochemical cell | |
US20180243727A1 (en) | Hydrogen production using hybrid photonic-electronic materials | |
Pang et al. | Synthesis of α-Bi2Mo3O12/TiO2 nanotube arrays for photoelectrochemical COD detection application | |
Hu et al. | Facile coengineering of oxygen defects and highly active {110} facets in TiO2 nanorods for efficient water splitting | |
Syrek et al. | Anodic titanium oxide layers modified with gold, silver, and copper nanoparticles | |
Cho et al. | Self-assembled gold nanoparticle–mixed metal oxide nanocomposites for self-sensitized dye degradation under visible light irradiation | |
Iwantono et al. | Influence of Ag ion adsorption on the photoactivity of ZnO nanorods for dye-sensitized solar cell application | |
Chen et al. | Color TiO2 materials as emerging catalysts for visible-NIR light photocatalysis, a review | |
Lipińska et al. | Influence of annealing atmospheres on photoelectrochemical activity of TiO2 nanotubes modified with AuCu nanoparticles | |
CN102557130A (zh) | 一种制备二氧化钛纳米花阵列薄膜的方法 | |
Balgude et al. | Metal oxides for high-performance hydrogen generation by water splitting | |
CN108505098A (zh) | Pt负载富硫二硫化钼边界位点修饰二氧化钛纳米管阵列的制备方法 | |
CN107413338A (zh) | 一种金属铑纳米颗粒改性二氧化钛纳米管阵列光催化材料的制备方法 | |
CN108889315A (zh) | 一种MoS2/TiO2异质结构薄膜光催化剂的制备方法 | |
CN102468361B (zh) | 一种具有宽波范围响应的光电催化双功能电极的制备方法 | |
CN108607546B (zh) | 二氧化钛-碳复合载体负载铂的电催化剂及其制备方法 | |
Namoos et al. | Methods and strategies for producing porous photocatalysts | |
Maslov et al. | Structural features and photoelectrocatalytic properties of bismuth-doped titanium oxides |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171201 |
|
RJ01 | Rejection of invention patent application after publication |