CN113293383B - 一种钨酸铋/羟基氧化铟复合光电极及其制备方法和应用 - Google Patents
一种钨酸铋/羟基氧化铟复合光电极及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种钨酸铋/羟基氧化铟复合光电极及其制备方法和应用,属于防腐材料技术领域。本发明采用热蒸发法在基底的表面沉积Bi2O3,经煅烧得到Bi2WO6光电极,再经电化学沉积法引入InOOH,有利于促进Bi2WO6光电极的载流子分离和转移,大幅降低了载流子的复合速率,最终制备得到的Bi2WO6/InOOH复合光电极对太阳能光谱具有较强的光响应,能够有效捕获可见光,且能有效加速电极界面的水氧化速率。将本发明提供的Bi2WO6/InOOH复合光电极用于碳钢防腐,能够促使光生电子在碳钢表面的有效集聚,有效提升光生电子向碳钢的注入效率,使碳钢的自腐蚀电位负移,从而增强碳钢的抗腐蚀能力。
Description
技术领域
本发明涉及防腐材料技术领域,尤其涉及一种钨酸铋/羟基氧化铟复合光电极及其制备方法和应用。
背景技术
碳钢的腐蚀电势较低,耐腐蚀能力较弱,因此迫切需要开展碳钢防腐蚀的相关技术研究。光电化学防腐技术作为一种新型的腐蚀防护技术,能够利用n型半导体在光照条件下产生的光生电子注入到碳钢基体上,使其电势低于腐蚀电势,从而使碳钢进入不发生腐蚀的阴极保护区。该过程不牺牲半导体电极,理论上其具有较长的使用寿命,且太阳光能量取之不尽用之不竭,是一种重要的绿色防护方法。
在光电阴极防护方面,研究者们探讨了多种半导体光电极材料对碳钢的光致阴极保护的可能性,但目前仍主要局限于TiO2半导体。虽然TiO2结构稳定,成本低,但TiO2仅能吸收波长400nm以下的紫外光,难以有效利用太阳能中的可见光部分。基于此,开发可见光半导体光电极成为解决该问题的一种有效途径。近年来,Bi2WO6作为一种常见的半导体材料被人们广泛研究,其带隙为2.7eV,窄于TiO2的带隙,可以在可见光区域发生光能响应,但是,Bi2WO6作为半导体电极难以有效驱动水氧化,不利于碳钢的光生阴极保护,这是因为在光照条件下,电子和空穴同时产生,如果空穴无法氧化水,则电子易与空穴复合,导致电子难以转移至碳钢基体上,从而不利于碳钢的光生阴极保护。因此,如何提高Bi2WO6半导体电极表面的水氧化动力学是提高Bi2WO6光生阴极防腐的关键。
发明内容
本发明的目的在于提供一种钨酸铋/羟基氧化铟复合光电极及其制备方法和应用,本发明采用热蒸发法在基底的表面沉积Bi2O3,经煅烧得到Bi2WO6光电极,再经电化学沉积法引入InOOH,最终制备得到的Bi2WO6/InOOH复合光电极对太阳能光谱具有较强的光响应,且能有效加速电极界面水氧化速率,促使光生电子在碳钢表面的有效集聚,显著提升了碳钢的抗腐蚀能力。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种钨酸铋/羟基氧化铟复合光电极的制备方法,包括以下步骤:
采用热蒸发法在基底的表面沉积Bi2O3,得到Bi2O3光电极;
将钨酸铵的乙二醇溶液滴涂在所述Bi2O3光电极的表面,之后进行煅烧,得到Bi2WO6光电极;
将硝酸铟、高氯酸钠和水混合,得到电解质溶液;
在所述电解质溶液存在条件下,以所述Bi2WO6光电极为工作电极、Ag/AgCl电极为参比电极、铂网电极为对电极,进行恒电位沉积,得到钨酸铋/羟基氧化铟复合光电极。
优选地,在所述基底的表面沉积Bi2O3的操作参数包括:温度为20~30℃,真空度为4.5×10-5Pa,沉积速率为0.1~1nm/s,沉积时间为1~30min。
优选地,所述钨酸铵的乙二醇溶液中钨酸铵的浓度为0.5~2mol/L,所述钨酸铵的乙二醇溶液的滴涂量为50~200μL/cm2。
优选地,所述煅烧的温度为640~660℃,时间为2.5~3.5h。
优选地,所述煅烧后还包括:将煅烧所得电极进行洗涤,得到Bi2WO6光电极;所述洗涤用试剂为碱性溶液,所述碱性溶液的浓度为0.8~1.2mol/L。
优选地,所述电解质溶液中高氯酸钠的浓度为0.08~0.12mol/L,硝酸铟的浓度为5~10mmol/L。
优选地,所述恒电位沉积的电位为-0.5~-1V,时间为1~10min。
本发明提供了上述技术方案所述制备方法制备得到的钨酸铋/羟基氧化铟复合光电极,包括基底以及依次覆盖于所述基底表面的Bi2WO6层和InOOH层。
优选地,所述Bi2WO6层的厚度为1~50μm,所述InOOH层的厚度为50~1000nm。
本发明提供了上述技术方案所述钨酸铋/羟基氧化铟复合光电极在碳钢防腐中的应用。
本发明提供了一种钨酸铋/羟基氧化铟复合光电极的制备方法,包括以下步骤:采用热蒸发法在基底的表面沉积Bi2O3,得到Bi2O3光电极;将钨酸铵的乙二醇溶液滴涂在所述Bi2O3光电极的表面,之后进行煅烧,得到Bi2WO6光电极;将硝酸铟、高氯酸钠和水混合,得到电解质溶液;在所述电解质溶液存在条件下,以所述Bi2WO6光电极为工作电极、Ag/AgCl电极为参比电极、铂网电极为对电极,进行恒电位沉积,得到钨酸铋/羟基氧化铟复合光电极。本发明采用热蒸发法在基底的表面沉积Bi2O3,经煅烧得到Bi2WO6光电极,再经电化学沉积法引入InOOH,有利于促进Bi2WO6光电极的载流子分离和转移,大幅降低了载流子的复合速率,最终制备得到的Bi2WO6/InOOH复合光电极对太阳能光谱具有较强的光响应,能够有效捕获可见光,且能有效加速电极界面的水氧化速率。将本发明提供的Bi2WO6/InOOH复合光电极用于碳钢防腐,能够促使光生电子在碳钢表面的有效集聚,有效提升光生电子向碳钢的注入效率,使碳钢的自腐蚀电位负移,从而增强碳钢的抗腐蚀能力。此外,本发明提供的方法工艺简单,效率高,成本低。
附图说明
图1为实施例1制备的Bi2WO6光电极和Bi2WO6/InOOH复合光电极与碳钢耦联后在暗态和光照下的开路电位-时间曲线图;
图2为纯碳钢在暗态条件下以及纯碳钢与实施例2制备的Bi2WO6光电极或Bi2WO6/InOOH复合光电极耦合后在光照条件下的塔菲尔曲线图。
具体实施方式
本发明提供了一种钨酸铋/羟基氧化铟复合光电极的制备方法,包括以下步骤:
采用热蒸发法在基底的表面沉积Bi2O3,得到Bi2O3光电极;
将钨酸铵的乙二醇溶液滴涂在所述Bi2O3光电极的表面,之后进行煅烧,得到Bi2WO6光电极;
将硝酸铟、高氯酸钠和水混合,得到电解质溶液;
在所述电解质溶液存在条件下,以所述Bi2WO6光电极为工作电极、Ag/AgCl电极为参比电极、铂网电极为对电极,进行恒电位沉积,得到钨酸铋/羟基氧化铟复合光电极。
本发明采用热蒸发法在基底的表面沉积Bi2O3,得到Bi2O3光电极。本发明对所述基底的种类没有特殊限定,采用本领域技术人员熟知的基底即可,具体可以为FTO导电玻璃或钛板。在本发明中,所述基底在使用前优选进行洗涤和干燥,以保证其表面洁净;所述洗涤优选包括依次进行的水洗、乙醇洗和丙酮洗,所述洗涤优选在超声条件下进行,具体是将基底依次置于水、乙醇和丙酮中进行超声清洗;所述干燥优选为采用高纯氮气吹干。
在本发明中,在所述基底的表面沉积Bi2O3的操作参数包括:温度优选为20~30℃,具体是在室温条件下进行沉积;真空度优选为4.5×10-5Pa,沉积速率优选为0.1~1nm/s,更优选为0.1~0.2nm/s;沉积时间优选为1~30min,更优选为10~15min。在本发明的实施例中,具体是在室温条件下,将Bi2O3靶材放置于钽舟中,并将反应室内的压力抽真空至4.5×10-5Pa,在外加电流的作用下Bi2O3靶材以0.1~1nm/s沉积速率蒸发,沉积于基底的表面,得到Bi2O3光电极。
得到Bi2O3光电极后,本发明将钨酸铵的乙二醇溶液滴涂在所述Bi2O3光电极的表面,之后进行煅烧,得到Bi2WO6光电极。在本发明中,所述钨酸铵的乙二醇溶液中钨酸铵的浓度优选为0.5~2mol/L,更优选为0.2~1mol/L;所述钨酸铵的乙二醇溶液的滴涂量优选为50~200μL/cm2,更优选为80~100μL/cm2。本发明优选将钨酸铵的乙二醇溶液的滴涂量控制在上述范围,确保钨酸铵过量,以便氧化铋完全转化为钨酸铋。本发明对所述硝酸钴溶液的滴涂方式没有特殊限定,采用本领域技术人员熟知的滴涂方式、保证硝酸钴溶液涂覆均匀即可。
将钨酸铵的乙二醇溶液滴涂在所述Bi2O3光电极的表面后,本发明通过煅烧得到Bi2WO6光电极。在本发明中,所述煅烧的温度优选为640~660℃,更优选为650℃;时间优选为2.5~3.5h,更优选为3h。在本发明中,所述煅烧优选在马弗炉中进行。在本发明中,煅烧过程中,钨酸铵转化为氧化钨,高温条件下氧化钨和氧化铋发生固相反应,生成钨酸铋。
在本发明中,所述煅烧后优选还包括:将煅烧所得电极进行洗涤,得到Bi2WO6光电极。在本发明中,所述洗涤用试剂优选为碱性溶液,更优选为氢氧化钠溶液;所述碱性溶液的浓度优选为0.8~1.2mol/L,更优选为1mol/L;所述洗涤的方式优选为将煅烧所得电极浸泡于所述碱性溶液中,所述浸泡的时间优选为40~120min,更优选为50~60min。本发明通过洗涤去除煅烧后所得电极表面的残余的WO3。
本发明将硝酸铟、高氯酸钠和水混合,得到电解质溶液。在本发明中,所述电解质溶液中高氯酸钠的浓度优选为0.08~0.12mol/L,更优选为0.1mol/L;硝酸铟的浓度优选为5~10mmol/L。本发明对所述硝酸铟、高氯酸钠和水混合时的加料顺序以及混合方式没有特殊限定,保证各组分充分混合均匀即可,本发明优选将硝酸铟加入到高氯酸钠的水溶液中,混合得到电解质溶液。
得到Bi2WO6光电极和电解质溶液后,本发明在所述电解质溶液存在条件下,以所述Bi2WO6光电极为工作电极、Ag/AgCl电极为参比电极、铂网电极为对电极,进行恒电位沉积,得到钨酸铋/羟基氧化铟复合光电极。在本发明中,所述恒电位沉积的电位优选为-0.5~-1V,更优选为-0.5~-0.6V;时间优选为1~10min,更优选为5~8min。在本发明中,所述恒电位沉积沉积过程中,溶液中的氢离子被还原,导致局部溶液pH值增加,使电极表面的三价铟离子与氢氧根离子发生沉淀反应,生成羟基氧化铟。
本发明提供了上述技术方案所述制备方法制备得到的钨酸铋/羟基氧化铟复合光电极,包括基底以及依次覆盖于所述基底表面的Bi2WO6层和InOOH层。在本发明中,所述Bi2WO6层的厚度优选为1~50μm,所述InOOH层的厚度优选为50~1000nm。
本发明提供了上述技术方案所述钨酸铋/羟基氧化铟复合光电极在碳钢防腐中的应用。本发明对所述应用没有特殊限定,采用本领域技术人员熟知的方式应用即可。
下面将结合本发明中的实施例,对本发明中的技术方案进行清楚、完整地描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
将基底(具体为FTO导电玻璃)置于超声清洗器中分别经水洗、乙醇洗和丙酮洗,之后用高纯氮气吹干待用;
在室温(25℃)条件下通过热蒸发法在基底的表面沉积Bi2O3,具体是将Bi2O3靶材放置于钽舟中,并将反应室内的压力抽真空至4.5×10-5Pa,在外加电流的作用下Bi2O3靶材以0.1nm/s的沉积速率沉积10min,得到Bi2O3光电极;
将钨酸铵溶于乙二醇中,得到浓度为1mol/L的钨酸铵的乙二醇溶液;用移液枪移取100μL所述钨酸铵的乙二醇溶液滴涂在Bi2O3光电极表面(钨酸铵的乙二醇溶液的滴涂量为80μL/cm2),之后在650℃马弗炉中煅烧3h,取出后在1mol/L的氢氧化钠溶液中浸泡60min,以去除残余的WO3,得到Bi2WO6光电极;
将硝酸铟加入到浓度为0.1mol/L的高氯酸钠溶液中,得到电解质溶液,所述电解质溶液中硝酸铟的浓度为5mmol/L;
在所述电解质溶液存在条件下,以Bi2WO6光电极为工作电极、Ag/AgCl电极为参比电极、铂网电极为对电极,在-0.5V偏压条件下沉积5min,得到钨酸铋/羟基氧化铟复合光电极,记为Bi2WO6/InOOH复合光电极。
将腐蚀池中的碳钢与光阳极池中的Bi2WO6光电极或Bi2WO6/InOOH复合光电极通过铜线相连,研究二者在可见光间断照射条件下开路电位变化情况。图1为实施例1制备的Bi2WO6光电极和Bi2WO6/InOOH复合光电极与碳钢耦联后在暗态和光照下的开路电位-时间曲线图,由图1可知,暗态时,开路电位较正,当可见光照射的时候,与Bi2WO6光电极耦合的碳钢电极的开路电位正移,而与Bi2WO6/InOOH复合光电极耦合的碳钢电极的开路电位出现负移,这说明Bi2WO6光电极不仅不能保护碳钢,反而会加速碳钢的腐蚀,而与Bi2WO6/InOOH复合光电极耦合的碳钢电极的开路电位负移,说明Bi2WO6/InOOH复合光电极上的光生电子可以转移至碳钢表面,从而使耦合的碳钢电极的开路电位负移,进而实现了碳钢的光生阴极保护。
实施例2
将基底(具体为FTO导电玻璃)置于超声清洗器中分别经水洗、乙醇洗和丙酮洗,之后用高纯氮气吹干待用;
在室温(25℃)条件下通过热蒸发法在基底的表面沉积Bi2O3,具体是将Bi2O3靶材放置于钽舟中,并将反应室内的压力抽真空至4.5×10-5Pa,在外加电流的作用下Bi2O3靶材以0.2nm/s的沉积速率沉积15min,得到Bi2O3光电极;
将钨酸铵溶于乙二醇中,得到浓度为0.5mol/L的钨酸铵的乙二醇溶液;用移液枪移取150μL所述钨酸铵的乙二醇溶液滴涂在Bi2O3光电极表面(钨酸铵的乙二醇溶液的滴涂量为100μL/cm2),之后在650℃马弗炉中煅烧3h,取出后在1mol/L的氢氧化钠溶液中浸泡60min,以去除残余过剩的WO3,得到Bi2WO6光电极;
将硝酸铟加入到浓度为0.1mol/L的高氯酸钠溶液中,得到电解质溶液,所述电解质溶液中硝酸铟的浓度为10mmol/L;
在所述电解质溶液存在条件下,以Bi2WO6光电极为工作电极、Ag/AgCl电极为参比电极、铂网电极为对电极,在-0.6V偏压条件下沉积8min,得到钨酸铋/羟基氧化铟复合光电极,记为Bi2WO6/InOOH复合光电极。
图2为纯碳钢在暗态条件下以及纯碳钢与实施例2制备的Bi2WO6光电极或Bi2WO6/InOOH复合光电极耦合后在光照条件下的塔菲尔曲线图,电解液为3.5wt%NaCl溶液。由图2可知,纯碳钢在3.5wt%NaCl溶液中的腐蚀电势为-0.46V,当将腐蚀池中的碳钢与光阳极池中的Bi2WO6光电极耦联后,腐蚀电位正移至-0.38V,而与Bi2WO6/InOOH复合光电极耦联后,腐蚀电位发生负移,达到-0.63V,再次说明光照条件下的Bi2WO6光电极不能保护碳钢,而Bi2WO6/InOOH复合光电极则能保护碳钢。因此,InOOH的负载对提升Bi2WO6的光生阴极防护性能至关重要。
以上所述仅是本发明的优选实施方式,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润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (8)
1.一种钨酸铋/羟基氧化铟复合光电极的制备方法,包括以下步骤:
采用热蒸发法在基底的表面沉积Bi2O3,得到Bi2O3光电极;
将钨酸铵的乙二醇溶液滴涂在所述Bi2O3光电极的表面,之后进行煅烧,得到Bi2WO6光电极;所述钨酸铵的乙二醇溶液中钨酸铵的浓度为0.5~2mol/L,所述钨酸铵的乙二醇溶液的滴涂量为50~200µL/cm2;所述煅烧的温度为640~660℃,时间为2.5~3.5h;
将硝酸铟、高氯酸钠和水混合,得到电解质溶液;
在所述电解质溶液存在条件下,以所述Bi2WO6光电极为工作电极、Ag/AgCl电极为参比电极、铂网电极为对电极,进行恒电位沉积,得到钨酸铋/羟基氧化铟复合光电极。
2.根据权利要求1所述的制备方法,其特征在于,在所述基底的表面沉积Bi2O3的操作参数包括:温度为20~30℃,真空度为4.5×10-5Pa,沉积速率为0.1~1nm/s,沉积时间为1~30min。
3.根据权利要求1所述的制备方法,其特征在于,所述煅烧后还包括:将煅烧所得电极进行洗涤,得到Bi2WO6光电极;所述洗涤用试剂为碱性溶液,所述碱性溶液的浓度为0.8~1.2mol/L。
4.根据权利要求1所述的制备方法,其特征在于,所述电解质溶液中高氯酸钠的浓度为0.08~0.12mol/L,硝酸铟的浓度为5~10mmol/L。
5.根据权利要求1或4所述的制备方法,其特征在于,所述恒电位沉积的电位为-0.5~-1V,时间为1~10min。
6.权利要求1~5任一项所述制备方法制备得到的钨酸铋/羟基氧化铟复合光电极,包括基底以及依次覆盖于所述基底表面的Bi2WO6层和InOOH层。
7.根据权利要求6所述的钨酸铋/羟基氧化铟复合光电极,其特征在于,所述Bi2WO6层的厚度为1~50μm,所述InOOH层的厚度为50~1000nm。
8.权利要求6或7所述钨酸铋/羟基氧化铟复合光电极在碳钢防腐中的应用。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108126689A (zh) * | 2017-12-20 | 2018-06-08 | 江苏大学 | 一种富含氧缺陷的Bi2WO6/In2O3异质结复合光催化剂的制备方法及用途 |
CN109440130A (zh) * | 2018-11-29 | 2019-03-08 | 山东大学 | 一种大尺寸的纳米多孔BiVO4光阳极及其制备方法与应用 |
CN110465286A (zh) * | 2019-06-21 | 2019-11-19 | 广东工业大学 | 一种表面氧空位缺陷修饰的钨酸铋光催化剂及其制备方法和应用 |
CN110565111A (zh) * | 2019-07-24 | 2019-12-13 | 台州学院 | 一种六角柱型WO3/Bi2WO6复合光电极薄膜的制备方法 |
-
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- 2020-11-03 CN CN202011207214.8A patent/CN113293383B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108126689A (zh) * | 2017-12-20 | 2018-06-08 | 江苏大学 | 一种富含氧缺陷的Bi2WO6/In2O3异质结复合光催化剂的制备方法及用途 |
CN109440130A (zh) * | 2018-11-29 | 2019-03-08 | 山东大学 | 一种大尺寸的纳米多孔BiVO4光阳极及其制备方法与应用 |
CN110465286A (zh) * | 2019-06-21 | 2019-11-19 | 广东工业大学 | 一种表面氧空位缺陷修饰的钨酸铋光催化剂及其制备方法和应用 |
CN110565111A (zh) * | 2019-07-24 | 2019-12-13 | 台州学院 | 一种六角柱型WO3/Bi2WO6复合光电极薄膜的制备方法 |
Non-Patent Citations (2)
Title |
---|
"Photodegradation of Malachite Green by Nanostructured Bi2WO6 Visible Light-Induced Photocatalyst";Yijie Chen等;《International Journal of Photoenergy》;20121231;第1-7页 * |
"可见光响应Bi2WO6薄膜的制备与光电化学性能";张士成 等;《物理化学学报》;20070131;第23卷(第1期);第111-115页 * |
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