CN108043388B - 一种铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂及其制备方法与应用 - Google Patents
一种铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂及其制备方法与应用 Download PDFInfo
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明公开了一种铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂及其制备方法与应用。该双层壁纳米管阵列具有内层壁多孔、外层壁光滑的特殊形貌,质量百分比化学成分组成:铝:3.05~6.01%、钒:2.35~2.87%、氧:20.14~30.83%,其余为钛。本发明具有规整的独立管壁阵列结构、内壁多孔外壁光滑的特殊形貌、良好的可见光响应、快速电子传输通道以及较大的吸附性能,其可见光催化性能较纯钛纳米管阵列显著增强。本发明在太阳光的利用效率和光生电子空穴分离能力方面潜力巨大,能够广泛应用于光催化及光电催化废水治理、大气净化等方面。
Description
技术领域
本发明属于环境功能材料技术领域,具体涉及一种铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂及其制备方法。
背景技术
近年来,TiO2纳米管因其空间有序分散性、单通道电子传输能力及与基底间良好的电化学接触等特点在太阳能电池、光催化、光解水、药物运输以及传感器等领域拥有广阔应用前景,引起了研究者们的广泛关注。
在TiO2纳米管的主要合成方法中,电化学阳极氧化应用最为广泛,具有操作简单、通用性强、成本低、形态可控性良好等巨大优势。而TiO2纳米管的性能在很大程度上取决于结晶度和纳米管的表面积。TiO2纳米管的表面积可以通过改变形貌结构来调控,例如,管壁多孔、竹节状、树枝状和双壁等特殊形貌的纳米管,相比于管壁完整且光滑的纳米管,拥有更大的比表面积,更强的吸附能力,展现出更好的性能。然而现有技术的制备过程较为复杂,多采用几步阳极氧化法,或使用氢氟酸等环境不友好试剂,所制备的纳米管阵列可见光响应能力弱,对太阳光的利用率低。因此,能简易制备可见光响应的特殊形貌纳米管阵列有望成为环境污染深度处理技术及太阳能电池、光解水制氢等领域应用的最有效能源转化材料之一。
发明内容
本发明的目的在于克服现有技术所面临的特殊形貌纳米管阵列制备复杂、使用试剂不环保、所制备的纳米管阵列管壁共用、对太阳光利用率低以及氧化膜易脱离基体不利回收等缺点,提供了一种铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂及其制备方法。
本发明采用两电极体系,将预电化学抛光的合金钛片TC4作为阳极进行阳极氧化后煅烧结晶的方法,通过对阳极氧化条件的调控实现双层壁且内壁为多孔壁的特殊形貌结构,制备了具有可见光响应的铝、钒共掺杂双层多孔壁钛合金纳米管阵列光催化剂。其制备方法简单、形貌规则整齐、孔隙结构丰富、具有优异的可见光响应能力。同时氧化层与基体结合紧密,有利于后期回收复用等。
本发明目的通过以下技术方案来实现:
一种铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂,该双层壁纳米管阵列具有内层壁多孔、外层壁光滑的形貌,质量百分比化学成分组成:Al:3.05~6.01%、V:2.35~2.87%、O:20.14~30.83%,其余为Ti。
一种铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的制备方法,包括以下步骤:
(1)钛合金预处理:将钛合金TC4加工成片状,依次放入无水乙醇和去离子水中超声,室温干燥;
(2)电化学抛光:采用两电极体系,阴极为纯钛片、阳极为钛合金TC4,两电极间距1~4cm,电解液为含氯离子的乙二醇溶液,在直流恒压下室温抛光至镜面光滑,抛光过程伴随匀速搅拌,取出后依次放入无水乙醇和去离子水中超声,室温干燥;
(3)阳极氧化:采用两电极体系,阴极为纯钛片、阳极为步骤(2)处理后的钛合金TC4,两电极间距2~4cm,电解液为含氟化铵(NH4F)和去离子水(H2O)的乙二醇溶液,在直流恒压下阳极氧化,搅拌,无需维持电解液恒温,阳极氧化结束后放入无水乙醇中浸泡20~40min,在室温条件下自然干燥,得到无定形铝、钒共掺杂钛合金纳米管阵列,所述NH4F浓度为0.3wt%~0.7wt%;所述H2O体积为1~3vol%;所述电解液体积为58~62mL;
(4)锐钛矿铝、钒共掺杂双层多孔壁钛合金纳米管阵列的制备:将无定形铝、钒共掺杂钛合金纳米管阵列置于马弗炉中高温煅烧,空气气氛,得到锐钛矿铝、钒共掺杂双层多孔壁钛合金纳米管阵列。
进一步地,步骤(1)所述的钛合金TC4为双相合金,其化学成分质量分数组成:铝(Al)5.5~6.8%,钒(V)3.5~4.5%,铁(Fe)≤0.30%,碳(C)≤0.10%,氮(N)≤0.05%,氢(H)≤0.015%,氧(O)≤0.20%,其余为Ti;
所述的超声清洗时间为15~30min,所述室温下干燥的温度为20~35℃,干燥时间为1~3h。
进一步地,步骤(2)中,所述的阴极纯钛片有效面积为350~450mm2(背面为胶带覆盖),阳极钛合金TC4有效面积为2×350~450mm2;
所述的含氯离子的乙二醇溶液的溶质包括氯化锂(LiCl)、氯化钠(NaCl)、氯化钾(KCl)、氯化钙(CaCl2)、氯化镁(MgCl2),氯离子浓度为0.8~1.2mol/L。
进一步地,步骤(2)中,所述的电化学抛光电压范围为25~35V,抛光时间为5~20min,所述的室温抛光的温度为20~30℃,所述匀速搅拌的搅拌速度为50~80r/min;
所述的超声清洗时间为15~30min,所述室温下干燥的温度为20~35℃,干燥时间为1~3h。
进一步地,步骤(3)中,所述的钛合金(TC4)待阳极氧化面积为2×350~450mm2。
进一步地,步骤(3)中,所述的阳极氧化电压范围为30~90V,阳极氧化时间为1~4h,所述的室温阳极氧化,其电解液初始温度为18~22℃,无需维持电解液恒温,所述搅拌的搅拌速度为30~50r/min;
所述的无水乙醇浸泡时间为1~3h,所诉室温下干燥温度为20~35℃,时间为10~20h。
进一步地,步骤(4)中,所述的煅烧温度为400~600℃,煅烧时间为1~4h,升温速率为1~5℃/min。
进一步地,所述煅烧的具体步骤为:升温程序为先以2~4℃/min的速率从室温升至240~260℃,在245~255℃恒温25~35min,再以0.5~1.5℃/min的速率升至400~600℃,恒温1~4h,最后以1~5℃/min速率降至室温。
一种铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂应用于废水治理或大气净化。
与现有技术相比,本发明具有如下优势:
本发明具有独特的内层壁多孔、外层壁光滑的双壁纳米管阵列结构特征和优异的可见光催化性能。其制备方法简单、成本低廉、可同步实现可见光响应元素原位掺杂及多孔双壁纳米管阵列的构建、管壁独立、与基体结合紧密利于催化剂回收,相较其他方法制得的纳米管阵列有着更丰富的孔隙结构和可见光响应能力,故其在可见光下表现出较纯钛纳米管阵列更高的光催化活性。该催化剂能够广泛应用在光催化或光电催化治理废水、净化大气等方面。
附图说明
图1是本发明铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的XRD图;
图2a和图2b是本发明铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的能量色散X射线光谱图EDS;其中,图2a是TC4钛合金表面的能量色散X射线光谱图EDS;图2b是双层多孔壁钛合金纳米管阵列的能量色散X射线光谱图EDS;
图3a~图3d是本发明铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的场发射扫描电镜图FE-SEM:其中,图3a为双层多孔壁钛合金纳米管阵列顶部形貌图,图3b为双层多孔壁钛合金纳米管阵列侧壁形貌图,图3c为双层多孔壁钛合金纳米管阵列场发射透射电镜图HR-TEM:图3d为双层多孔壁钛合金纳米管阵列比表面积及孔径分布图;
图4是本发明铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的紫外可见漫反射光谱图DRS;
图5是本发明铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂对邻苯二甲酸二丁酯(DBP)的可见光催化降解效果图。
具体实施方式
下面结合具体实施例对本发明作进一步地具体详细描述,但本发明的实施方式不限于此,对于未特别注明的工艺参数,可参照常规技术进行。
实施例1
(1)钛合金预处理:将合金钛片TC4加工成20mm×30mm×2mm的片状,依次放入无水乙醇和去离子水中各超声20min,室温干燥2h,所用合金钛片TC4的主要化学成分组成为:Ti:89.43%、Al:6.01%、V:2.64%、C:1.92%。
(2)电化学抛光:采用两电极体系,阴极为纯钛片(有效面积400mm2)、阳极为钛合金TC4,待抛光面积2×400mm2,两电极间距3cm,电解液为NaCl的乙二醇溶液,氯离子浓度为1mol/L。在30V直流恒压下室温抛光10min,依次放入无水乙醇和去离子水中各超声20min,室温干燥2h。
(3)阳极氧化:采用两电极体系,阴极为纯钛片(有效面积400mm2)、阳极为步骤(2)处理后的抛光合金钛片TC4,待阳极氧化面积为2×400mm2,两电极间距3cm,电解液为0.5wt%NH4F、2vol%H2O的乙二醇溶液60mL。在70V直流恒压下氧化3h,缓慢搅拌,电解液初始温度为20℃,无需维持恒温。阳氧结束后放入无水乙醇中浸泡20min,室温下自然干燥,得到双层壁无定形铝、钒共掺杂钛合金纳米管阵列。
实施例2
(1)钛合金预处理:将合金钛片TC4加工成20mm×30mm×2mm的片状,依次放入无水乙醇和去离子水中各超声20min,室温干燥2h,所用合金钛片TC4的主要化学成分组成为:Ti:89.43%、Al:6.01%、V:2.64%、C:1.92%。
(2)电化学抛光:采用两电极体系,阴极为纯钛片(有效面积400mm2)、阳极为钛合金TC4,待抛光面积2×400mm2,两电极间距3cm,电解液为NaCl的乙二醇溶液,氯离子浓度为1mol/L。在30V直流恒压下室温抛光10min,依次放入无水乙醇和去离子水中各超声20min,室温干燥2h。
(3)阳极氧化:采用两电极体系,阴极为纯钛片(有效面积400mm2)、阳极为步骤(2)处理后的抛光合金钛片TC4,待阳极氧化面积为2×400mm2,两电极间距3cm,电解液为0.5wt%NH4F、2vol%H2O的乙二醇溶液60mL。在50V直流恒压下氧化1h,缓慢搅拌,电解液初始温度为20℃,无需维持恒温。阳氧结束后放入无水乙醇中浸泡20min,室温下自然干燥,得到单层壁无定形铝、钒共掺杂钛合金纳米管阵列。
实施例3
(1)锐钛矿铝、钒共掺杂双层多孔壁钛合金纳米管阵列的制备:将实施例1中制备的双层壁无定形铝、钒共掺杂钛合金纳米管阵列置于马弗炉中500℃高温煅烧2h,空气气氛。升温程序为先以2℃/min的速率从室温升至250℃,250℃恒温30min,以1℃/min的速率升至500℃,恒温2h,最后以3℃/min速率降至室温,得锐钛矿铝、钒共掺杂双层多孔壁钛合金纳米管阵列,记为DW-ATNTAs。
(2)锐钛矿铝、钒共掺杂单层多孔壁钛合金纳米管阵列的制备:将实施例2中制备的单层壁无定形铝、钒共掺杂钛合金纳米管阵列置于马弗炉中500℃高温煅烧2h,空气气氛。升温程序为先以2℃/min的速率从室温升至250℃,250℃恒温30min,以1℃/min的速率升至500℃,恒温2h,最后以3℃/min速率降至室温,得锐钛矿铝、钒共掺杂单层多孔壁钛合金纳米管阵列,记为SW-ATNTAs。
(3)不同光催化剂的XRD图(图1),表明所制备的铝、钒共掺杂双层多孔壁钛合金纳米管阵列为纯锐钛矿晶相。EDS能谱图(图2a~图2b),表明成功实现铝、钒双金属元素的掺杂。从扫描电镜、透射电镜以及比表面积及孔径分布(图3a~图3d)表明双层多孔壁钛合金纳米管阵列结构的成功制备。从UV-Vis漫反射图谱(图4)中可以得知所制备的锐钛矿铝、钒共掺杂双层多孔壁钛合金纳米管阵列具有良好的可见光响应。
实施例4
光催化活性评价:采用邻苯二甲酸二丁酯(DBP)为模型污染物,比较不同光催化剂的可见光催化活性。光催化降解反应在自制的光催化反应装置中进行,催化剂有效面积为400mm2(与光源垂直),光源光强为可见光AM1.5G(100mW/cm2);DBP的初始浓度为5mg/L,溶液总体积为100mL;开启光源之前先进行1h的暗吸附;通过高效液相色谱测定溶液中剩余DBP的浓度来评价其光催化性能。实验结果表明:DW-ATNTAs光催化剂表现出比SW-ATNTAs、纯钛纳米管阵列(记为TNTAs)更高的可见光催化活性(图5),在180min内DBP的去除率接近100%,表现出优异的可见光催化活性。
以上实施例仅用以说明本发明的技术方案而非严格的条件限制,本领域的普通人员应当理解,可以在不偏离权利要求书所限定的本发明的精神和范围上对其细节或形式对其做出各种变化。
Claims (9)
1.一种铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的制备方法,其特征在于,包括以下步骤:
(1)钛合金预处理:将钛合金TC4加工成片状,依次放入无水乙醇和去离子水中超声,室温干燥;
(2)电化学抛光:采用两电极体系,阴极为纯钛片、阳极为钛合金TC4,两电极间距1~4cm,电解液为含氯离子的乙二醇溶液,在直流恒压下室温抛光至镜面光滑,抛光过程伴随匀速搅拌,取出后依次放入无水乙醇和去离子水中超声,室温干燥;
(3)阳极氧化:采用两电极体系,阴极为纯钛片、阳极为步骤(2)处理后的钛合金TC4,两电极间距2~4 cm,电解液为含氟化铵(NH4F)和去离子水(H2O)的乙二醇溶液,在直流恒压下阳极氧化,搅拌,无需维持电解液恒温,阳极氧化结束后放入无水乙醇中浸泡20~40min,在室温条件下自然干燥,得到无定形铝、钒共掺杂钛合金纳米管阵列,所述NH4F浓度为0.3wt%~0.7wt%;所述H2O体积为1~3vol%;所述电解液体积为58~62mL;
(4)锐钛矿铝、钒共掺杂双层多孔壁钛合金纳米管阵列的制备:将无定形铝、钒共掺杂钛合金纳米管阵列置于马弗炉中高温煅烧,空气气氛,得到锐钛矿铝、钒共掺杂双层多孔壁钛合金纳米管阵列;
所述双层壁纳米管阵列具有内层壁多孔、外层壁光滑的形貌,质量百分比化学成分组成:Al: 3.05~6.01%、V:2.35~2.87%、O:20.14~30.83%,其余为Ti;
步骤(3)中,所述的阳极氧化电压范围为30~90V,阳极氧化时间为1~4h,所述的室温阳极氧化,其电解液初始温度为18~22℃,无需维持电解液恒温,所述搅拌的搅拌速度为30~50r/min。
2.根据权利要求1所述铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的制备方法,其特征在于步骤(1)所述的钛合金TC4为双相合金,其化学成分质量分数组成:铝(Al)5.5~6.8%,钒(V)3.5~4.5%,铁(Fe)≤0.30%,碳(C)≤0.10%,氮(N)≤0.05%,氢(H)≤0.015%,氧(O)≤0.20%,其余为Ti;
所述的超声清洗时间为15~30min,所述室温下干燥的温度为20~35℃,干燥时间为1~3h。
3.根据权利要求1所述铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的制备方法,其特征在于,步骤(2)中,所述的阴极纯钛片有效面积为350~450 mm2,背面为胶带覆盖,阳极钛合金TC4有效面积为2×350~450 mm2;
所述的含氯离子的乙二醇溶液的溶质包括氯化锂(LiCl)、氯化钠(NaCl)、氯化钾(KCl)、氯化钙(CaCl2)、氯化镁(MgCl2),氯离子浓度为0.8~1.2mol/L。
4.根据权利要求1所述铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的制备方法,其特征在于,步骤(2)中,所述的电化学抛光电压范围为25~35V,抛光时间为5~20min,所述的室温抛光的温度为20~30℃,所述匀速搅拌的搅拌速度为50~80r/min;
所述的超声清洗时间为15~30min,所述室温下干燥的温度为20~35℃,干燥时间为1~3h。
5.根据权利要求1所述铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的制备方法,其特征在于步骤(3)中,所述的钛合金TC4待阳极氧化面积为2×350~450 mm2。
6.根据权利要求1所述铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的制备方法,其特征在于,所述的无水乙醇浸泡时间为1~3 h,所诉室温下干燥温度为20~35℃,时间为10~20h。
7.根据权利要求1所述铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的制备方法,其特征在于,步骤(4)中,所述的煅烧温度为400~600℃,煅烧时间为1~4 h,升温速率为1~5℃/min。
8.根据权利要求1所述铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂的制备方法,其特征在于,所述煅烧的具体步骤为:升温程序为先以2~4℃/min的速率从室温升至240~260℃,在245~255℃恒温25~35 min,再以0.5~1.5℃/min的速率升至400~600℃,恒温1~4 h,最后以1~5℃/min速率降至室温。
9.权利要求1所述制备方法制备得到的一种铝、钒共掺杂双层多孔壁钛合金纳米管阵列可见光催化剂应用于废水治理或大气净化。
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