CN102625780A - 钒酸铋颗粒和获得其的方法 - Google Patents
钒酸铋颗粒和获得其的方法 Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 40
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title 1
- 239000002243 precursor Substances 0.000 claims abstract description 16
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- 230000000996 additive effect Effects 0.000 claims abstract description 12
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 6
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
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- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004438 BET method Methods 0.000 claims description 3
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
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- 239000004141 Sodium laurylsulphate Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
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- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 241000338702 Cupido minimus Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 208000034189 Sclerosis Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
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- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
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Abstract
本发明的主题是获得化学式BiVO4的颗粒的方法,其中使铋和钒前体和至少一种选自包括至少一个烃链的硫酸盐或膦酸盐类型的表面活性剂的添加剂在低于50℃的温度反应。本发明的主题还是化学式BiVO4的颗粒,其的表面具有Br?nsted位点。
Description
本发明涉及由式BiVO4的钒酸铋构成的光催化颗粒的领域。
钒酸铋BiVO4因其光催化性能而众所周知。由于其性能由可见光激活的事实,其是特别有价值的。在可见光辐射的作用下,产生电子空穴对,其将有助于氧化还原反应的催化,这特别地导致有机化合物的降解。其的结果是抗污、净化或杀菌性能。
Yang
et al (Material Chemistry and Physics 114, 2009, pp 69-72)描述了在180℃至(ou)220℃的温度BiVO4颗粒的水热合成。在这些合成条件下,添加表面活性剂,十二烷基硫酸钠(SDS),使在单斜白钨矿(scheelite)相中改善结晶成为可能。
发明人现在已经发现在不属于水热合成的条件下,在较低的温度进行合成使得原始颗粒能够被获得,其具有超酸性能,诱发降解有机化合物的更有效的机理。
本发明的主题因此是用于获得式BiVO4的颗粒的方法,其中使铋和钒前体和至少一种选自包括至少一个烃链的硫酸盐或膦酸盐类型的表面活性剂的添加剂在低于50℃的温度反应。
本发明的主题还是化学式BiVO4的颗粒,其的表面包含Brønsted位点。颗粒特别地能够通过根据本发明的方法获得。
相比于严格的式BiVO4,所获得的颗粒的化学式可以略变化。特别地,摩尔比Bi/V可以典型地在0.96和1.04之间变化。虽然如此,在不背离本发明的范围的情况下,氧的化学计量也可略变化。
反应优选地在环境温度,特别地在15和30℃之间,优选地在20和25℃之间进行。反应优选地在大气压进行。
反应优选地在含水溶液中举行,这避免使用毒性溶剂或对环境不利的溶剂。
优选地使用单个铋前体和单个钒前体。这些前体优选地是盐或氧化物。
至少一种铋前体选自硝酸铋或氯化铋。硝酸铋五水合物是特别优选的。至少一种钒前体优选地选自钒酸铵或钒酸钠。氧化钒也可作为前体。
硫酸盐或膦酸盐类型的添加剂的烃链优选地是直链或支链烷基链,其包含6-20个碳原子,特别地10-16个碳原子。足够长的烃链使得减慢从正方相至单斜相的转变成为可能。添加剂的反离子可以例如是钠离子(Na+),锂离子(Li+),钾离子(K+)或铵离子。如果实际上"硫酸盐"或"膦酸盐"也被理解为包括共轭酸的话,它也可是质子(H+)。十二烷基硫酸钠和十四烷基膦酸已经被证明是特别有利的。
在根据本发明使用的非水热条件下,添加剂已经被证明能在颗粒的表面上产生Brønsted酸位点。这些位点的存在导致有机化合物非常强吸附到颗粒的表面上,这导致通过更有效的降解机理,这些化合物的更快速降解。添加剂的存在另外使产生特别的形态和显著地提高颗粒的比表面积成为可能。
铋和钒前体的相对比例优选地被选择以便原子比Bi/V在0.9和1.1之间,特别地在0.95和1.05之间。比例等于1是优选的。这些条件使促进BiVO4相的形成,同时防止其它确定的化合物形成成为可能。
钒和/或铋的摩尔浓度优选地在0.01和0.5mol/L之间,特别地在0.05和0.2mol/L之间。添加剂的浓度优选地在0.005和0.05mol/L之间,特别地在0.008和0.02mol/L之间。在反应期间的pH一般地是酸性的,典型地低于2或甚至接近于1。
反应的持续时间可以是数小时至几天,典型地2小时至1星期。
在反应的末端,通过已知的技术,例如通过离心分离,回收颗粒。颗粒优选地被洗涤。
在使颗粒与吡啶接触后,通过红外光谱可以确定Brønsted位点的存在。Brønsted位点将导致与在以下波长的区域中峰的存在有关的吡啶的质子化:1640cm-1,1540cm-1和1490cm-1。
这些位点的存在导致有机化合物,特别地吡啶,的强吸附。特别地,结果是高于150℃的化学吸附的吡啶的完全解吸的温度。通过使颗粒的样品与吡啶接触至各种温度并且根据本文其余部分中详述的实验规程通过红外光谱评价吡啶的存在,可以确定该温度。
Brønsted位点的存在还导致在颗粒的极端(extreme)表面中过量浓度的铋。这种过量的浓度特别地导致大于1.5,特别地大于1.7的通过X射线光电子光谱(XPS)测量的Bi/V比。
颗粒的平均直径优选地是500纳米至5微米,特别地700纳米至2微米。如在下文中表明的,尽管颗粒的微米级的尺寸,添加剂的添加使获得非常高的比表面积成为可能。因此不再需要使用纳米级的颗粒,其可以代表与其待吸入的能力相关的毒理学问题。此外,因为促进电子-空穴复合,小尺寸的纳米颗粒可以在光催化方面是不太有效的。
所获得的颗粒具有在导带和价带之间的大约2.4eV的间隙。波长大约515纳米的辐射由此能激活光催化反应。
根据本发明的颗粒优选地包括白钨矿类型的单斜相晶体和锆石类型的正方(quadratic)相晶体。尽管关于光催化方面更活性的相是白钨矿相,似乎其它相的存在使增加光催化效率成为可能。这种效应,或许由于电子和空穴之间更好的分离,已经特别地在二氧化钛方面进行了描述,对此锐钛矿和金红石相的混合物证明是特别高活性的,而金红石相本身具有低活性。单斜相优选地是主相——在其质量比例大于50%,特别地60%或65%的意义上。
颗粒的比表面积,借助于BET法通过氮吸附确定的,优选地是大于或等于10m2/g。
本发明的主题还是涂布有至少一层的包括通过根据本发明的方法获得的颗粒或包括根据本发明的颗粒的层的基材。
借助于无机粘结剂,颗粒优选地被粘结到基材。有机粘结剂实际上可能通过BiVO4颗粒的光催化作用而快速降解。
无机粘结剂优选地基于氧化物,特别地二氧化硅。它可能由二氧化硅组成,特别地通过溶胶-凝胶类型方法获得的。为此,有机金属前体,例如原硅酸四乙氧基酯(TEOS),冷凝在基材的表面上。溶胶可以通过浸涂、电池-涂布(cell-coating)或喷涂来沉积。通常,需要热处理步骤以便除去溶剂,从而使该层致密化并且使其在机械性上强化。为促进由污染物质接近颗粒,粘结剂,特别地二氧化硅,可以被制成多孔的。它可以特别地具有中孔(mesopores),其中孔的直径为2至50纳米。这样的中孔可以借助于结构化剂或"模板"获得,一般地基于两亲分子如表面活性剂或嵌段共聚物。这些试剂具有使其本身组织成胶束的能力,围绕该胶束,前体将凝结和冷凝。其它金属氧化物,如氧化铝或氧化锆,也可通过类似方法获得并且用作粘结剂。
粘结剂也可基于硅烷或硅酮。
基材优选地由玻璃构成并且特别地是玻璃板。然而可以使用任何类型的材料,如陶瓷,金属或聚合有机材料,特别地板、薄膜或纤维的形式。基材优选地是透明或半透明的。为此,玻璃或聚合有机物质如聚碳酸酯或聚甲基丙烯酸甲酯是优选的。优选地,玻璃板具有至少一个大于1米,或甚至大于2或3米的维度。它的厚度优选地是0.5至19mm,特别地3至9mm。玻璃可以特别地是钠钙硅类型的,或者是硼硅酸盐或铝硼硅酸盐类型的。玻璃可以是澄清的或超澄清的或者被着色的,例如着蓝色,青铜色,灰色,琥珀色,粉红色等。玻璃板可以特别地被退火,硬化,韧化,或弯曲。基材可以是平坦的或弯曲的。
除含根据本发明的颗粒的层外,基材可以,在同侧或另一侧上,涂布有至少一层的其它层或甚至堆叠的层。
它可以例如由低-发射堆叠的层(特别地包括至少一层的银层)组成,所述低-发射堆叠的层控制日光,是抗反射的,抗静电的,导电体,反射的(例如用于反射镜的银层),或者可以由油漆或漆料的层组成。特别地有可能在包含根据本发明的颗粒的层的下面沉积一或多层的子层(sous-couches)。其可能特别地由作为来自基材的碱(alkalis)的迁移的屏障的层组成,所述碱金属可以构成光催化的毒剂(poison)。它也可由被设计以减弱从含根据本发明的颗粒的层反射的光和/或在反射中获得中性或略带蓝色的着色的一层或若干层组成。在这种情况下,优选地,通过具有高和低折射率的交替的层,使用干涉现象。
含根据本发明的颗粒的层优选地是离基材最远的层并且由此与环境空气接触。这样,它将更能够与大气污染物相互作用并且实现其净化或自洁功能。
本发明的主题还是玻璃制品,特别地用于建筑物、车辆或家具,镜,由玻璃构成的墙壁覆盖物,门或玻璃隔板,包括至少一种根据本发明的基材。
玻璃制品可以特别地是单层的(single)或多层的(multiple)(例如双层(double)或三层(triple)玻璃制品)或者可以被层合。
这样的玻璃制品具有自洁,防污和杀菌或净化或脱臭性能。因为其被可见光激活,它可以实现其功能,包括在建筑物或车辆内部的功能——在紫外辐射低的情况下。
这些性能也可被用于在除玻璃制品以外的材料中发挥优势。含根据本发明的颗粒的层可以特别地沉积在纤维材料,例如矿棉、毡(felts)、垫(mats)、织物、织造或非织造网的表面上,特别地用作过滤器(filtres)。
在阅读实施方案的以下非限制性实例后,将更好地理解本发明。
图1是根据本发明的颗粒的扫描电镜照片。
图2是对比颗粒的扫描电镜照片。
图3是叠加分别根据本发明的颗粒和对比颗粒的两个红外光谱。
制备25ml的水溶液A,其包含在1.5M硝酸溶液中的硝酸铋五水合物Bi(NO3)3.5H2O。
另外,制备25mL的水溶液B,其包含钒酸钠NaVO3。在其各自溶液中铋和钒的浓度是0.2M。
0.146g的十二烷基硫酸钠(SDS)被添加到溶液A。
然后混合两个溶液并且在磁力搅拌的情况下在环境温度保持1周。
通过离心分离回收所形成的颗粒,用水洗涤并随后在氮气物流下干燥。
以相同方式获得对比样品,唯一的例外是没有添加SDS并且钒前体是V2O5。对于根据本发明的样品,使用相同前体,还制备样品,并且证明比对比样品具有甚至更低的光催化活性。
X射线衍射分析表明颗粒包含大约70wt%的白钨矿类型的单斜相和30wt%的正方锆石相(phase quadratique zircon)。
借助于BET法如根据氮吸附测定的比表面积是12m2/g。对比样品的比表面积低于3m2/g。
根据本发明的颗粒的形态在图1中举例说明。有可能观察以非常特征性薄的薄片形式的表面的结构化。当与在没有添加SDS的情况下合成的对比样品的颗粒相比时,这种特别的形态非常不同于图2的形态。该形态也非常不同于由Yang等(Material Chemistry and Physics 114, 2009, pp 69-72)借助于水热合成获得的。
通过X射线光电子光谱(XPS)测量的Bi/V比是1.8,其源于在颗粒的极端表面处大过量浓度的铋。结晶表面平面由此是富集铋的平面。相反地,对于对比样品测量的相同比例仅仅是1.3。
该过量浓度或许与更高的表面酸性和颗粒表面中的Brønsted位点的存在有关。
以下列方式表明Brønsted位点的存在:
在200℃在二级(secondary)真空下加热通过压缩粉末获得的粒料2小时以便清洗任何杂质的表面。然后,在1托的压力,使粒料接触过量的吡啶。然后,使样品经受初级并随后二级(secondary)真空,以便消除任何存在的任何物理吸附的吡啶并且以便仅仅保留化学吸附的吡啶。
图3的红外光谱是为根据本发明的样品(曲线A)和对比样品(点画曲线B)获得的那些。存在可以由具有波数1640cm-1,1540cm-1和1490cm-1的峰看出,后者是吡啶的质子化的特征。这种质子化证明了在颗粒的表面和吡啶之间强的O-H-N键,一种其起源是Brønsted位点的存在的键。另一方面,在对比样品的红外光谱上,没有看见吡啶的质子化,这表明不存在Brønsted位点。另一方面,对于波数1593cm-1,1574cm-1和1440cm-1,明显观察到配位键的存在。这些键是路易斯(Lewis)位点的存在的标志。
红外光谱由此表明吡啶和根据本发明的颗粒之间的键比由未用SDS合成的对比样品的颗粒观察到的键强很多,这由于Brønsted位点的存在。
这的结果是,在根据本发明的颗粒的情况下,完全解吸吡啶的更高的温度,特别地高于150℃。通过在各种温度加热先前制备的粒料15分钟:50,100并随后150℃,可以确定完全解吸的温度。该加热的结果是化学吸附的吡啶的解吸。通过红外光谱评价仍然化学吸附的吡啶的存在与否。在对比样品的情况下,全部解吸在50至100℃的温度发生。另一方面,在150℃的温度下,根据本发明的样品仍然包含化学吸附的吡啶。
通过光催化的有机化合物的降解机理可以随后是在可见区中的光谱方法。
为做到这一点,将颗粒的样品添加到若丹明(rhodamine)B的水溶液。选择若丹明B的浓度以便在黑暗中吸附后,溶液的吸光度是大约1。在黑暗中搅拌1小时后,混合物暴露到可见光。
调整添加到溶液的颗粒的数量以便对于根据本发明的样品和对比样品来说,颗粒的表面面积相同。考虑比表面积的差别,根据本发明的颗粒的数量(0.125g)比对比颗粒的数量(0.5g)小很多。尽管如此,在两种情况中,在320分钟的末端,若丹明B完全降解。本发明由此使对于数量少很多的颗粒获得等量活性,或者对于相同数量的颗粒获得高很多的活性成为可能。
对比样品所获得的光谱特征为在位于波长555纳米处的峰的吸收强度的降低。这样的变化是由于水溶液中存在的自由基造成的分子的共轭结构的降解特有的。
另一方面,根据本发明的样品所获得的光谱本质表征为吸收峰向较低波长移动,证明连续的N-脱乙基反应。这种降解机理涉及在颗粒的表面处并且不仅在溶液中存在的自由基。这一方面证实了通过根据本发明的颗粒的有机分子的较好的吸附。另一方面,这种机理,其涉及在不存在任何液体介质的情况下,例如当其由净化气体或使表面自洁组成时,颗粒表面上存在的自由基的反应是更加有效的。换言之,由于Brønsted位点的存在,由根据本发明的颗粒造成的有机分子的较好的吸附将极大地促进其随后的降解。
含根据本发明的颗粒的层如下制备。将含颗粒和十二烷基硫酸盐添加剂的混合物通过旋转涂布沉积在澄清的钠钙硅玻璃基材上。在通过暴露于紫外辐射24小时添加剂已经降解后,获得由BiVO4的颗粒组成的层。通过用颗粒/THF(四氢呋喃)溶液旋转涂布,还制备含对比颗粒的层。
以下述方式测量光催化活性:
- 切出5×5cm2样品,
- 对于在4000和400cm-1之间的波数,通过FTIR测量红外光谱,以便制备参考光谱,
- 沉积硬脂酸:60微升的以10g/L的速率溶解在乙醇中的硬脂酸的溶液,通过旋转涂布沉积在样品上,
- 通过FTIR测量红外光谱,测量在3000和2700cm-1之间CH2-CH2键的伸长谱带的面积,
- 暴露于辐射,即UV+可见光或仅仅可见光。所用的灯是模拟太阳辐射的灯(Suntest类型的氙弧灯),向其添加抗UV滤光器,视情况需要,
- 在暴露30分钟的连续周期后的硬脂酸层的光降解,随后测量在2980和2825cm-1之间CH2-CH3键的伸长谱带的面积A。
硬脂酸的降解的标志是根据系数k,面积A随时间线性减少,所述系数k定义为是光催化活性。
在UV+可见光辐射下层的光催化活性是大约1.25×10-2×min-1。比较起来,在作为碱的屏障的层上沉积的15纳米厚的二氧化钛层的光催化活性仅仅是0.25×10-2×min-1。
在仅仅由可见光辐照的情况下,光催化活性是6.2×10-3×min-1。含对比颗粒(用添加剂合成)的层的光催化活性是0.6×10-3×min-1。在相同条件下二氧化钛的层的光催化活性是零。
根据本发明的颗粒由此使在由可见光辐照下获得具有非常高的光催化活性的层成为可能。
Claims (14)
1.用于获得化学式BiVO4的颗粒的方法,其中使铋和钒前体和至少一种选自包括至少一个烃链的硫酸盐或膦酸盐类型的表面活性剂的添加剂在低于50℃的温度反应。
2.根据权利要求1的方法,使得反应在环境温度进行。
3.根据前述权利要求中任一项的方法,使得反应在含水溶液中进行。
4.根据前述权利要求中任一项的方法,使得至少一种铋前体选自硝酸铋或氯化铋。
5.根据前述权利要求中任一项的方法,使得至少一种钒前体选自钒酸铵或钒酸钠。
6.根据前述权利要求中任一项的方法,使得硫酸盐或膦酸盐类型的添加剂的烃链是含6-20个碳原子的直链或支链烷基链。
7.化学式BiVO4的颗粒,其的表面包含Brønsted位点。
8.根据前述权利要求的颗粒,其的平均直径是500纳米至5微米。
9.根据权利要求7或8的颗粒,包括白钨矿类型的单斜相晶体和锆石类型的正方相晶体。
10.根据权利要求7至9中任一项的颗粒,其的比表面积,借助于BET法通过氮吸附确定的,大于或等于10m2/g。
11.涂布有至少一层的包括通过根据权利要求1至6中任一项的方法获得的颗粒或根据权利要求7至10中任一项的颗粒的层的基材。
12.根据前述权利要求的基材,使得借助于无机粘结剂将颗粒粘结到基材。
13.根据前述权利要求的基材,使得无机粘结剂是基于二氧化硅的。
14.玻璃制品,特别地用于建筑物、车辆或家具,镜,由玻璃构成的墙壁覆盖物,其包括至少一个根据前述基材权利要求之一的基材。
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PCT/FR2010/051794 WO2011023918A1 (fr) | 2009-08-31 | 2010-08-30 | Particules de vanadate de bismuth et leur procede d'obtention |
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