CN108855131A - 一种银-镍双金属掺杂二氧化钛纳米复合材料的制备和应用 - Google Patents
一种银-镍双金属掺杂二氧化钛纳米复合材料的制备和应用 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 138
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 13
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 11
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 27
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- 238000000034 method Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
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- 235000019445 benzyl alcohol Nutrition 0.000 abstract description 24
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract description 22
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- 150000001299 aldehydes Chemical class 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
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- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
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- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- -1 aromatic alcohols Chemical class 0.000 description 1
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- 239000012496 blank sample Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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Abstract
本发明公开了一种银‑镍双金属掺杂二氧化钛纳米复合材料的制备方法,先用过氧化氢处理二氧化钛得过钛酸钛络合物O2‑TiO2,在此基础上通过掺杂金属Ni和Ag,得到银‑镍双金属掺杂的二氧化钛纳米复合材料Ag‑N‑TiO2。与纯TiO2相比,Ag‑Ni‑TiO2用于催化氧化苯甲醇的反应中表现出更好的催化活性。实验结果表明,Ag‑Ni‑TiO2在1个大气压下,300W氙灯照射下,对苯甲醇的转换率可达98.45%,苯甲醛的产率可达94.17%,选择性可达93%,因此,复合材料Ag‑Ni‑TiO2在选择性光催化氧化芳香醛的反应中具有很好的应用前景。
Description
技术领域
本发明涉及一种TiO2基纳米复合材料,尤其涉及这一种银-镍双金属掺杂二氧化钛纳米复合材料Ag-Ni/TiO2的制备;主要用于芳香醇的催化氧化反应中。
背景技术
芳香醛是合成精细化学品和药物的重要组成部分,广泛应用于染料、香料、农药等领域。其中苯甲醛是最简单的具有活性羰基的芳香醛,是重要的有机反应中间体。在工业上,苯甲醛主要通过使用有害试剂(如Cr6 +,Mn7+,ClO4 -和Cl2)作为氧化剂的液相氧化甲苯来生产的。因此寻找一条环境友好的路线来生产苯甲醛引起了人们的兴趣。到目前为止,光催化技术是解决这个问题最有希望的途径。已经研究的各种光催化材料(CdS,ZnO,CeO2,BiOCl,C3N4,BiVO4),可以从各个方面满足人们的需求(活性,选择性,稳定性成本等)。例如,CdS是一种带隙较窄的经典半导体(Eg=2.4eV),但其容易受到轻度光腐蚀,产生有毒的Cd2+对造成环境损害。CeO2由于带隙能量较宽(Eg=3.2eV),太阳能利用效率较差,使得光催化活性普遍不理想。
TiO2是一种理想的光催化剂,具有良好的光催化活性,稳定性高,成本低,无毒性和较强的空穴氧化能力。然而,由于TiO2带隙(Eg=3.2eV)较宽,只能在紫外线照射(λ<387nm)下使用,仅利用5%的太阳光。现已经研究了各种方法来增强其在可见光下的活性。 例如,根据RaffaeleMarotta 报道,Cu2+掺杂的TiO2可以捕获电子,从而减少电子-空穴复合,并增加苯甲醇选择性氧化成苯甲醛的转化率。Yasuhiro Shiraishi研究了Fe3+掺杂的TiO2光催化剂可以实现较大的电荷分离,并能在环境温度下有效选择性氧化苯甲醇。然而,这些催化剂都只能响应紫外光,不能吸收可见光,且转化效率较低。
发明内容
本发明的目的是针对现有技术催化氧化苯甲醇转化成苯甲醛的反应存在转化率较低的问题,提供一种双金属掺杂Ag-Ni/TiO2纳米材料的制备方法;
中本发明的另一目的是提供该双金属掺杂Ag-Ni/TiO2纳米材料在光催化氧化苯甲醇制备苯甲醛的应用性能。
一、Ag-Ni/TiO2纳米材料的制备
(1)O2-TiO2的合成:将TBOT(钛酸四丁酯)用0~5℃的冷水沉淀,去离子水反复洗涤后,在磁力搅拌下加入去离子水和过氧化氢的混合溶液中,并保持体系在0~5℃下搅拌0.5~1h,得橙色过氧钛酸盐络合物;再将橙色过氧钛酸盐络合物加热至40~50℃反应3~4小时;反应液在80~100℃的空气烘箱中干燥10~15h,得到黄色固体物质;最后将黄色固体物质放入马弗炉中,以10℃/min的速率升温至250~300℃,煅烧1.5~2小时,得到橙色过钛酸钛络合物O2-TiO2;
过氧化氢为30%H2O2;去离子水和过氧化氢的混合溶液中,去离子水和过氧化氢的体积比为1:0.5~1:1。
(2)Ni-TiO 2前驱体的制备:将C4H6NiO4·4H2O(四水和乙酸镍)与橙色过钛酸钛络合物以1:100~1:10的质量比混合,加热至40~50℃反应3~4小时;反应液在80~100℃的空气烘箱中干燥10~15h,得到Ni-TiO2前驱体。
(3)Ag-Ni-TiO2的合成:在AgNO3的水溶液中加入NaBH4,搅拌15~20min后,再加入上述前驱体Ni-TiO2,搅拌混匀后将混合液在80~100℃空气烘箱中干燥10~15h,得黄色固体物质;然后将黄色固体物质置于马弗炉中,以10℃/分钟的速度升温至250~300℃,煅烧1.5~2小时,得到Ag-Ni-TiO2。
AgNO3与NaBH4的摩尔比为2:1~3:1;AgNO3与Ni-TiO2的质量比为1:200~1:100。
所得样品Ag-Ni-TiO2中,Ag的掺杂浓度为0.25~0.5wt%,Ni的掺杂浓度为0.5~2.0wt%。
二、Ag-Ni-TiO2复合材料表征
1、透射电镜分析
使用配备有整体球的UV-vis分光光度计(PuXin TU-1901)将BaSO4作为空白样品。通过场发射扫描电子显微镜(FE-SEM,Ultra Plus,Carl Zeiss)和透射电子显微镜(TEM,FEITecnai F20显微镜)对光催化剂的形貌进行表征。
图1(a)为Ag(0.5%)-Ni(1%) - TiO2的透射图。可以看出,复合材料具有均匀的表面且具有小球结构,平均粒径为39nm。
图1(b)为Ag(0.5%)-Ni(1%)-TiO2的高倍透射图。0.3520nm和0.2378nm处的特征晶粒充分表明锐钛矿TiO2的(101)和(004)面。说明了金属掺杂并未改变TiO2的晶型。
2、XRD分析
使用Bragg-Brentano Rigaku D / MAX-2200 / PCX衍射仪进行粉末XRD测量。它采用40 kV x 20 mA的电流供电,并配有垂直测角仪,采用Ni过滤CuKα辐射,使用θ-θ几何结构。在2θ= 20~80°范围内收集数据并获得X射线衍射(XRD)图。
图2为TiO2(a)、O2-TiO2(b)和(c)Ag(0.5%)-Ni(1%)-TiO2的XRD图谱。分析了催化剂的XRD以研究样品的晶体结构和晶粒大小。图2可观察到,有尖锐,强烈的衍射峰表明了有结晶良好的样品形成。我们观察到在2θ处:25.28°,38.58°,48.05°,53.92°,55.06°,62.73°和75.03°,与JCPDS文件No.21-1272(标准卡片)进行比较对应的晶面是(101),(112),(020),(010),(211),(420),和(215)。可以判断Ag(0.5%)-Ni(1%)-OTiO2复合材料属于锐钛矿相。由于金属含量较低,所以在光催化剂的衍射图中没有观察到Ag和Ni的衍射峰。根据Scherrer公式计算样品的平均晶粒尺寸。
式中D是沿着垂直于晶面方向的晶粒直径,θ是布拉格衍射角,β是以弧度为单位的半峰宽度,λ是所使用的X射线波长(0.154nm)。计算得样品的平均晶粒尺寸约为39 nm。
3、紫外漫反射分析
图3显示了TiO2,O2-TiO2,Ag-TiO2,Ni-TiO2和Ag-Ni-TiO2样品相应的UV-vis漫反射光谱(DRS)。由图3发现,纯TiO2在可见光波段不被吸收,仅在紫外区域具有强烈的吸收。随着氧被引入到TiO2的晶格中,得到的O2-TiO2被红移到约420nm。在Ag掺杂后,在可见光区(500nm)出现光响应,这应该归因于银纳米颗粒的典型表面等离子体激元共振效应。与Ag-TiO2相比,Ni-TiO2催化剂在可见光波段有较强的吸收,并略有增加。而Ag-Ni-TiO2催化剂在600nm可见光区域表现出最强的吸收。
4、光致发光光谱分析
光致发光(PL)光谱使用F97Pro荧光分光光度计记录,激发波长为300nm,在325-525nm范围内记录光致发光光谱,扫描速度为3000nm / min,PMT电压为650V,激发狭缝宽度为10nm,发射狭缝宽度为10nm。
图4为TiO2,O2-TiO2,Ni-TiO2和Ag-Ni-TiO2光催化剂的光致发光光谱(PL)。与TiO2相比,O2-TiO2显示较低的强度,表明氧改性样品O2-TiO2中载体重组得到改善。当Ni掺杂浓度增加到1.0wt%时,光致发光强度逐渐降低。而当Ag的掺杂浓度为0.5wt%,Ni掺杂浓度为1.0wt%时,Ag-Ni-TiO2表现出最低的PL强度,这是因为催化剂氧化过程形成更多的氧空位和表面缺陷。
5、光电化学(PEC)性能
光电流和电化学阻抗谱(EIS)测量是在含有0.5mol/L Na2SO4(pH=7.5)水溶液的标准三电极电池中进行的,铂电极和饱和Ag/AgCl电极分别作为对电极和参比电极,选择LED灯(λ> 420 nm)作为光源,所有电化学测量均在室温下进行。工作电极由氟化锡(FTO)导体玻璃制成,将少量萘酚溶液(10μl)滴在导电玻璃上,将固体样品(10mg)分散在乙二醇中并超声处理20分钟,然后将其滴在涂有萘酚溶液的FTO导电玻璃上,工作电极在红外光照射下光照1小时。光电化学测试,偏压选取0.6V,通过FTO背面的照明,照明面积约为1.0cm-2。
图5显示了电化学阻抗谱(EIS)奈奎斯特图,以进一步确定Ag-Ni-TiO2催化剂相对于O2-TiO2和TiO2在改善载流子转移方面的优势。一般来说,奈奎斯特圆的半径越小,电荷转移阻力就越小。与TiO2相比,Ag-Ni-TiO2显示更小的半圆,表明更快的界面电荷转移到电子受体。表明AgNPs和NiNPs是促进电子-空穴对有效分离和转移的有效途径。因此,可以显示出更好的光催化性能。
三、光催化活性
在50mL自制反应器中进行醇的光催化选择性氧化实验。通常,将光催化剂(80mg)和0.5mmol苯甲醇(反应物)和三氟甲苯(5mL)溶解在石英玻璃瓶(40mm×25mm)中,然后将玻璃瓶注入到反应器中。通入纯O 2使悬浮液饱和5分钟,然后将氧气压力保持在2个大气压。使用300W氙灯(CEL-HXF300,北京金光)作为光源在磁力搅拌下照射悬浮液。反应后,将溶液离心除去催化剂颗粒。取上清液用气相色谱仪(GC9600,中国)进行分析并鉴定有机产物。最后,通过用无水乙醇和去离子水反复洗涤来回收催化剂,并在80℃的烘箱中干燥过夜以进行循环光活性测试。光催化反应温度由室温下的循环水系统控制。 AgNO3,AO,TBA,BQ等自由基清除剂分别被用作光生电子,光生空穴,羟自由基和超氧自由基的清除剂。除了自由基清除剂(0.1mmol)加入到反应体系之外,细节类似于光催化氧化苯甲醇的实验,有机产物经GC9600分析鉴定。醇转化率,醛产率和醛选择性计算如下:
转化率 % = [(C0-C1)/C0]×100% (1)
产率 % = (C2/C0) ×100% (2)
选择性 % = [C2/(C0-C1)] ×100% (3)
其中,C0是照射前的底物醇的初始量;C1是照射1小时后的底物醇的量; C2是照射反应后相应的醛的量。
图6a比较了纯TiO2与掺杂了不同含量Ni的TiO2光催化选择性氧化苯甲醇的性能。1%Ni-TiO2样品的苯甲醇氧化性能较好,转化率为93.04%,产率为88.67%,选择性为93.43%。
为了探索银纳米粒子掺杂对光催化反应的影响,用不同含量的银纳米粒子掺杂Ni-TiO2催化剂,结果如图6b所示。发现只有当Ag,Ni 共掺杂的时候对光催化过程的效率产生了积极影响并增加了催化剂表面的活性位点。其中Ag(0.5%)-Ni(1%)-TiO2对苯甲醇氧化性能最好,转化率为98.45%,产率为94.17%,选择性不变。
图7显示了不同底物对测试结果的影响,分别使用对甲氧基苯甲醇,对氯苯甲醇和苯甲醇作为底物。结果表明,苯环上具有吸电子取代基,如对氯苄醇,转化率高达90%,苯环上有给电子取代基,如对甲氧基苄醇,转化率高达90%。无论取代基是吸电子还是电子给体,只要能够帮助醇的α-氢活化,相应的醇都会有很好的转化率。但是,苯甲醇的转化率和产率及选择性仍然高于其它芳香醇。
为了说明Ag-Ni-TiO2催化剂在苯甲醇选择性氧化反应中的可重复使用性,进行了四个循环实验。结果如图8所示,经过四个循环实验,可以看出,产率、转化率、选择性没有明显变化,说明该物质在所用反应条件下具有良好的稳定性。
为了说明Ag-Ni-TiO2在苯甲醇光催化氧化反应中可能的反应机理,采用不同的自由基清除剂进行了一系列的对照实验。结果发现,当BQ(对苯醌)和IPA(异丙醇)的清除剂被加入到苯甲醇反应体系的光催化氧化中时,苯甲醇的转化率略有下降。当OA(草酸)和AgNO3加入到苯甲醇反应体系的光催化氧化中,苯甲醇的转化率迅速下降。基于以上结果,苯甲醇选择氧化成苯甲醛主要是由e-和h +共同作用引发的。
综上所述,本发明用过氧化氢处理二氧化钛得过钛酸钛络合物O2-TiO2,在此基础上通过掺杂金属Ni和Ag,得到银-镍双金属掺杂的二氧化钛纳米复合材料Ag-N-TiO2。与纯TiO2相比,Ag- Ni- TiO2用于催化氧化苯甲醇的反应中表现出更好的催化活性。实验结果表明,Ag- Ni- TiO2在1个大气压下,300W氙灯照射下,对苯甲醇的转换率可达98.45%,苯甲醛的产率可达94.17%,选择性可达 93%,因此,复合材料Ag-Ni-TiO2在选择性光催化氧化芳香醛的反应中具有很好的应用前景。
附图说明
图1为Ag(0.5%) - Ni(1%) - TiO2的透射图(a)及Ag(0.5%) - Ni(1%) - TiO2的高倍透射图(b)。
图2为TiO2(a)、O2-TiO2(b)、Ag(0.5%) - Ni(1%) - TiO2(c)的XRD图谱。
图3为TiO2(a)、O2-TiO2(b)、Ag(0.5%) - TiO2(c)、Ni(1%) - TiO2(d)和Ag(0.5%)- Ni(1%) - TiO2(e)的紫外漫反射图。
图4为TiO2(a)、O2-TiO2(b)、Ni(1%) - TiO2(c)和Ag(0.5%) - Ni(1%) - TiO2(d)的PL光谱。
图5为在0.5M Na2SO4(pH=7.35)中在开路电位下模拟太阳光照射的阻抗图。
图6为不同比例的Ni-TiO2(a)及不同比例的Ag-Ni-TiO2(b)的光催化氧化性能图。
图7为光催化氧化不同底物的性能图。
图8为Ag-Ni-TiO2催化剂的循环性稳定性测试。
具体实施方式
下面通过具体实施例对本发明复合催化剂Ag-Ni-TiO2的制备、性能和应用做进一步说明。
实施例1
(1)O2-TiO2的合成:取3mL TBOT缓慢加入到50 mL冷水(5℃)中,立即产生白色沉淀;去离子水反复洗涤沉淀后,在磁力搅拌下将沉淀物加入到50ml去离子水和25ml H2O2的混合溶液中,保持温度为5℃下搅拌1小时,得橙色过氧钛酸盐络合物。再将橙色过氧钛酸盐络合物加热至50℃保持4小时;反应液在100℃的空气烘箱中干燥过夜,得到黄色固体物质。然后将黄色固体物质放入马弗炉中,以10℃/min的速率升温至300℃,煅烧处理2小时,得到0.7g橙色过钛酸钛络合物O2-TiO2;
(2)Ni-TiO 2前驱体的制备:将0.05g C4H6NiO4·4H2O(四水和乙酸镍)与上述制备的橙色过钛酸钛络合物O2-TiO2混合,加热至50℃反应3小时;反应液在100℃的空气烘箱中干燥10h,得到Ni-TiO2前驱体;
(3)Ag-Ni-TiO2的合成:取0.025g AgNO 3,溶解在50ml去离子水中,并加入0.04g NaBH4(AgNO 3 : NaBH 4 = 2:1),搅拌20分钟后,加入上述Ni-TiO 2前驱体, 搅拌混匀后将混合液在100℃空气烘箱中干燥过夜,得黄色固体物质。将黄色固体物质置于马弗炉中,以10℃/分钟的速度升温至300℃,煅烧2小时,得到Ag-Ni-TiO2。所得样品Ag-Ni-TiO2中,Ag的掺杂浓度为0.5wt%,Ni的掺杂浓度为1.0wt%,标记为:Ag(0.5%)-Ni(1.0%)-TiO2;
(4)Ag(0.5%)-Ni(1.0%)-TiO2的催化氧化苯甲醇的性能:在1个大气压下,300W氙灯照射下,对苯甲醇的转换率为98.45%,苯甲醛的产率为94.17%,选择性为 93.00%。
实施例2
(1)O2-TiO2的合成:同实施例1;
(2)Ni-TiO 2前驱体的制备:将0.1g C4H6NiO4·4H2O(四水和乙酸镍)与上述制备的的橙色过钛酸钛络合物O2-TiO2混合,再将橙色过氧钛酸盐络合物加热至50℃反应3小时;反应液在100℃的空气烘箱中干燥10h,得到Ni-TiO2前驱体;
(3)Ag-Ni-TiO2的合成:取0.025g AgNO 3,溶解在50ml去离子水中,并加入0.04g NaBH4(AgNO 3 : NaBH 4 = 2:1),搅拌20分钟后,加入上述Ni-TiO 2前驱体, 搅拌混匀后将混合液在100℃空气烘箱中干燥过夜,得黄色固体物质。将黄色固体物质置于马弗炉中,以10℃/分钟的速度升温至300℃,煅烧2小时,得到Ag-Ni-TiO2。所得样品Ag-Ni-TiO2中,Ag的掺杂浓度为0.5wt%,Ni的掺杂浓度为2.0wt%,标记为:Ag(0.5%)-Ni(2.0%)-TiO2;
(4)Ag(0.5%)-Ni(2.0%)-TiO2的催化氧化苯甲醇的性能:在1个大气压下,300W氙灯照射下,对苯甲醇的转换率为65.66%,苯甲醛的产率为60.31%,选择性为93.12%。
实施例3
(1)O2-TiO2的合成:同实施例1;
(2)Ni-TiO 2前驱体的制备:将0.025g C4H6NiO4·4H2O(四水和乙酸镍)与上述制备的橙色过钛酸钛络合物以1:100的质量比混合,再将橙色过氧钛酸盐络合物加热至50℃反应3~4小时;反应液在80~100℃的空气烘箱中干燥10h,得到 Ni-TiO2前驱体;
(3)Ag-Ni-TiO2的合成:取0.025g AgNO 3,溶解在50ml去离子水中,并加入0.04g NaBH4(AgNO 3 : NaBH 4 = 2:1),搅拌20分钟后,加入上述Ni-TiO 2前驱体, 搅拌混匀后将混合液在100℃空气烘箱中干燥过夜,得黄色固体物质。将黄色固体物质置于马弗炉中,以10℃/分钟的速度升温至300℃,煅烧2小时,得到Ag-Ni-TiO2。所得样品Ag-Ni-TiO2中,Ag的掺杂浓度为1.0wt%,Ni的掺杂浓度为1.0wt%,标记为:Ag(1%)-Ni(1%)-TiO2。
(4)Ag(1%)-Ni(1%)-TiO2的催化氧化苯甲醇的性能:在1个大气压下,300W氙灯照射下,对苯甲醇的转换率为90.03%,苯甲醛的产率为87.44%,选择性为93.27%。
Claims (6)
1.一种银-镍双金属掺杂二氧化钛纳米复合材料的制备方法,包括以下步骤:
(1)O2-TiO2的合成:将TBOT用0~5℃的冷水沉淀,去离子水反复洗涤后,在磁力搅拌下加入去离子水和过氧化氢的混合溶液中,并保持体系在0~5℃下搅拌0.5~1h,得橙色过氧钛酸盐络合物;再将橙色过氧钛酸盐络合物加热至40~50℃反应3~4小时;反应液在80~100℃的空气烘箱中干燥10~15h,得到黄色固体物质;最后将黄色固体物质放入马弗炉中,以10℃/min的速率升温至250~300℃,煅烧1.5~2小时,得到橙色过钛酸钛络合物O2-TiO2;
(2)Ni-TiO 2前驱体的制备:将C4H6NiO4·4H2O与橙色过钛酸钛络合物以1:100~1:10的质量比混合,加热至40~50℃反应3~4小时;反应液在80~100℃的空气烘箱中干燥10~15h,得到Ni-TiO2前驱体;
(3)Ag-Ni-TiO2的合成:在AgNO3的水溶液中加入NaBH4,搅拌15~20min后,再加入上述前驱体Ni-TiO2,搅拌混匀后将混合液在80~100℃空气烘箱中干燥10~15h,得黄色固体物质;然后将黄色固体物质置于马弗炉中,以10℃/分钟的速度升温至250~300℃,煅烧1.5~2小时,得到Ag-Ni-TiO2。
2.如权利要求1所述一种银-镍双金属掺杂二氧化钛纳米复合材料的制备方法,其特征在于:步骤(1)中,过氧化氢为30%H2O2;去离子水和过氧化氢的混合溶液中,去离子水和过氧化氢的体积比为1:0.5~1:1。
3.如权利要求1所述一种银-镍双金属掺杂二氧化钛纳米复合材料的制备方法,其特征在于:步骤(3)中,AgNO3与NaBH4 的摩尔比为2:1~3:1。
4.如权利要求1所述一种银-镍双金属掺杂二氧化钛纳米复合材料的制备方法,其特征在于:步骤(3)中,AgNO3与Ni-TiO2的质量比为1:200~1:100。
5.如权利要求1所述方法制备的银-镍双金属掺杂二氧化钛纳米复合材料,其特征在于:所得样品Ag-Ni-TiO2中,Ag的掺杂浓度为0.25~0.5wt%,Ni的掺杂浓度为0.5~2.0wt%。
6.如权利要求5所述一种银-镍双金属掺杂二氧化钛纳米复合材料作为光催化剂在催化氧化芳香醇的反应中。
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